U.S. patent number 9,733,584 [Application Number 15/089,218] was granted by the patent office on 2017-08-15 for toner.
This patent grant is currently assigned to CANON KABUSHIKI KAISHA. The grantee listed for this patent is CANON KABUSHIKI KAISHA. Invention is credited to Koji Abe, Toshihiko Katakura, Shiro Kuroki, Akane Masumoto, Katsuyuki Nonaka, Tsuneyoshi Tominaga.
United States Patent |
9,733,584 |
Masumoto , et al. |
August 15, 2017 |
Toner
Abstract
Provided is a toner that is improved in transferability as
compared to the related art and that keeps its effects through
repeated use. In particular, provided is a toner suppressed in
dependency on transfer current control. The toner includes a toner
particle including a surface layer containing an organosilicon
polymer and a resin having an ionic functional group, the
organosilicon polymer having a partial structure represented by the
following formula (1), the toner particle containing 5.0% or more
of the partial structure represented by the formula (1) per 1.000
silicon atom contained in the organosilicon polymer, the resin
having an ionic functional group having a pKa of 6.0 or more and
9.0 or less: R.sup.0--SiO.sub.3/2 (1) in the formula (1), R.sup.0
represents an alkyl group having 1 or more and 6 or less carbon
atoms, or a phenyl group.
Inventors: |
Masumoto; Akane (Yokohama,
JP), Nonaka; Katsuyuki (Mishima, JP), Abe;
Koji (Numazu, JP), Katakura; Toshihiko (Susono,
JP), Tominaga; Tsuneyoshi (Suntou-gun, JP),
Kuroki; Shiro (Suntou-gun, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
CANON KABUSHIKI KAISHA |
Tokyo |
N/A |
JP |
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Assignee: |
CANON KABUSHIKI KAISHA (Tokyo,
JP)
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Family
ID: |
57111800 |
Appl.
No.: |
15/089,218 |
Filed: |
April 1, 2016 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20160299447 A1 |
Oct 13, 2016 |
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Foreign Application Priority Data
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Apr 8, 2015 [JP] |
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2015-079249 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
G03G
9/0819 (20130101); G03G 9/09725 (20130101); G03G
9/0825 (20130101) |
Current International
Class: |
G03G
9/08 (20060101); G03G 9/097 (20060101) |
Field of
Search: |
;430/108.3,111.4 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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H03-089361 |
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Apr 1991 |
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JP |
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H09-179341 |
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Jul 1997 |
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JP |
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Other References
US. Appl. No. 15/089,197, filed Apr. 1, 2016, Shiro Kuroki. cited
by applicant.
|
Primary Examiner: Chapman; Mark A
Attorney, Agent or Firm: Fitzpatrick Cella Harper and
Scinto
Claims
What is claimed is:
1. A toner, comprising: a toner particle including a surface layer
derived from a resin particle, the resin particle containing a
resin having an ionic functional group and an acid dissociation
constant pKa of 6.0 to 9.0, the surface layer further comprising an
organosilicon polymer having a partial structure represented by
formula (1): R.sup.0--SiO.sub.3/2 (1) wherein R.sup.0 represents an
alkyl group having 1 to 6 carbon atoms, or a phenyl group, and a
ratio of a peak area for the partial structure represented by
formula (1) to a total peak area for the organosilicon polymer is
5.0% or more in a .sup.29Si-NMR measurement of a
tetrahydrofuran-insoluble matter of the toner particle.
2. A toner according to claim 1, wherein a ratio of a silicon atom
density dSi with respect to a total of 100.0 atomic % of a carbon
atom density dC, an oxygen atom density dO, and the silicon atom
density dSi on the surface of the toner particle is 1.0 to 28.6
atomic % in X-ray photoelectron spectroscopic analysis of a surface
of the toner particle.
3. A toner according to claim 1, wherein when 16 straight lines
that cross a cross-section of the toner particle are drawn so as to
pass through a midpoint of a long axis L that is a maximum diameter
of the cross-section of the toner particle and to form an equal
crossing angle at the midpoint (crossing angle: 11.25.degree.),
forming 32 line segments from the midpoint to a surface of the
toner particle, in X-ray photoelectron spectroscopic analysis of a
surface of the toner particle the surface layer on the 32 line
segments has an average thickness Dav. of 5.0 nm or more.
4. A toner according to claim 3, wherein a ratio of a number of the
line segments having thicknesses of 2.5 nm or less of the surface
layer is 20.0% or less.
5. A toner according to claim 1, wherein the resin having an ionic
functional group has a pKa of 7.0 to 8.5.
6. A toner according to claim 1, wherein R.sup.0 represents a
methyl group or an ethyl group.
7. A toner according to claim 1, wherein the resin having an ionic
functional group is a polymer A having a monovalent group
represented by formula (2): ##STR00012## where R.sup.1 represents a
hydroxy group, a carboxy group, an alkyl group having 1 to 18
carbon atoms, or an alkoxy group having 1 to 18 carbon atoms,
R.sup.2 represents a hydrogen atom, a hydroxy group, an alkyl group
having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18
carbon atoms, g represents an integer of 1 to 3, h represents an
integer of 0 to 3, and when h represents 2 or 3, h R.sup.1's may be
the same or different, and * represents a binding site in a main
chain structure of the polymer A.
8. A toner according to claim 1, wherein the resin particle
containing the resin having an ionic functional group has a median
diameter (D50) on a volume basis of 5 to 200 nm.
Description
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention relates to a toner for developing an
electrostatic charge image to be used in image forming methods,
such as electrophotography and electrostatic printing.
Description of the Related Art
As an electrophotographic apparatus using a toner, there are given
a laser printer and a copying machine. As a request from users with
respect to electrophotographic apparatus, such as a copying machine
and a printer, in recent years, there is a demand for the provision
of downsizing, high durability for supporting high-speed printing,
and an image of stable quality not depending on a usage environment
(temperature, humidity).
In electrophotography, a toner charged positively or negatively is
carried on a toner bearing member, an elestrostatic charge
image-bearing member is charged to form a potential difference
between an image portion and a non-image portion, and a toner on
the toner bearing member is developed onto the image portion of the
elestrostatic charge image-bearing member. The developed toner on
the elestrostatic charge image-bearing member is subjected to a
step (transfer step) of transferring the toner onto a transfer
member, such as paper, or an intermediate transfer member and
further transferring the toner onto a transfer member, and is fixed
onto the transfer member with heat and pressure.
When a toner image formed on the elestrostatic charge image-bearing
member by performing development is transferred onto the transfer
member in the transfer step, a transfer residual toner may remain
on the elestrostatic charge image-bearing member. In this case, it
is necessary to clean the elestrostatic charge image-bearing member
with a cleaning device to recover the transfer residual toner into
a waste toner container. However, due to the presence of the
cleaning device and the waste toner container, the apparatus is
increased in size, and the increase becomes an obstacle for
downsizing the apparatus. Therefore, there is a demand for further
improvement of transferability in order to achieve downsizing of
the apparatus.
Further, when a toner is transferred from the photosensitive member
onto the transfer material, the amount of a toner that remains on
the photosensitive member without being transferred onto the
transfer member, that is, the transfer residual toner changes
depending on the transfer current. In general, there is an optimum
range of the transfer current in which the amount of the transfer
residual toner becomes minimum. When the transfer current is lower
than the optimum current range, a transfer electric field is small
relative to attraction force between the toner and the
photosensitive member, and hence the toner does not move and the
amount of the transfer residual toner increases.
Meanwhile, when the transfer current is larger than the optimum
current range, discharge occurs in a toner layer to rather decrease
the transfer electric field, and hence the amount of the transfer
residual toner is increased. Thus, it is desired that the transfer
current be set to the lowest within the optimum current range.
However, the optimum current range changes also depending on the
charge quantity of a toner. In particular, when printing is not
performed for a long period of time under high humidity, a
reduction in charge quantity, and a change in attraction force
between the toner and the photosensitive member are liable to
occur, and hence the optimum range of the transfer current is
liable to change. In order to address this change, there is a
method involving determining a transfer current with an environment
detection device, such as a temperature and humidity sensor.
However, there is a concern that various control devices may be
complicated and increased in size. Therefore, there is a demand for
a toner having satisfactory transferability within a wide transfer
current range without a change in charge quantity even under high
temperature and high humidity.
Hitherto, as a method of improving transferability, there has been
given a method involving sticking an external additive to the
surface of a toner particle to decrease physical adhesive force
between a toner and a photosensitive member. However, when an image
is printed on a large number of sheets, the external additive is
embedded or detached to make a reducing effect on the adhesive
force insufficient, and hence it is difficult to keep
transferability. As a method of improving transferability, a method
has been considered, which involves uniformly covering the surface
of a toner particle with a silicon compound.
In Japanese Patent Application Laid-Open No. H03-089361, as a
method of covering the surface of a toner particle with a silicon
compound, there is a disclosure of a method of producing a
polymerized toner by adding a silane coupling agent to a reaction
system.
Further, in Japanese Patent Application Laid-Open No. H09-179341,
there is a disclosure of a polymerized toner having on the surface
thereof a coating film of a reaction product of a radical reactive
organosilane compound.
SUMMARY OF THE INVENTION
Investigations made by the inventors of the present invention have
found that, in the toner disclosed in Japanese Patent Application
Laid-Open No. H03-089361, the precipitation amount of a silane
compound onto the surface of the toner is insufficient, and the
toner is susceptible to improvement in terms of
transferability-improving effect. Further, it has been found that,
in the toner disclosed in Japanese Patent Application Laid-Open No.
H09-179341, its adhesive force changes due to moisture absorption
under a high-temperature and high-humidity environment, and the
transferability-improving effect is not sufficient, and hence the
toner is susceptible to improvement.
The present invention is directed to providing a toner that is
improved in transferability as compared to the related art and that
keeps its effects through repeated use. In particular, the present
invention is directed to providing a toner suppressed in dependency
on transfer current control.
In order to achieve the above-mentioned objects, the inventors of
the present invention have made extensive investigations, and as a
result, have found the following toner.
That is, according to one aspect of the present invention, there is
provided a toner including a toner particle including a surface
layer derived from a resin particle, wherein: the resin particle
contains a resin having: an ionic functional group, and an acid
dissociation constant pKa of 6.0 or more and 9.0 or less, the
surface layer further contains an organosilicon polymer; the
organosilicon polymer has a partial structure represented by the
following formula (1); R.sup.0--SiO.sub.3/2 (1) in the formula (1),
R.sup.0 represents an alkyl group having 1 or more and 6 or less
carbon atoms, or a phenyl group, in a .sup.29Si-NMR measurement of
a tetrahydrofuran-insoluble matter of the toner particle, the ratio
of a peak area for the partial structure represented by the formula
(1) to a total peak area for the organosilicon polymer is 5.0% or
more.
Further features of the present invention will become apparent from
the following description of exemplary embodiments with reference
to the attached drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a conceptual diagram for defining the surface thickness
of the surface of a toner containing an organosilicon compound.
FIG. 2 is a graph for showing an NMR measurement example of an
organosilicon compound in the present invention.
FIG. 3 is an illustration of an example of an electrophotographic
apparatus to which the present invention is applicable.
FIG. 4 is an illustration of a measurement apparatus of a charge
quantity in the present invention.
DESCRIPTION OF THE EMBODIMENTS
Preferred embodiments of the present invention will now be
described in detail in accordance with the accompanying
drawings.
A toner of the present invention includes a toner particle
including a surface layer derived from a resin particle containing
a resin having an ionic functional group. The surface layer further
contains an organosilicon polymer; and the organosilicon polymer
has a partial structure represented by the following formula (1).
In a .sup.29Si-NMR measurement of a tetrahydrofuran-insoluble
matter of the toner particle, the ratio of a peak area for the
partial structure represented by the formula (1) to a total peak
area for the organosilicon polymer is 5.0% or more, and the resin
having an ionic functional group has a pKa of 6.0 or more and 9.0
or less. The toner of the present invention having the
above-mentioned configuration has an excellent effect that a
transfer current range (hereinafter expressed as "transfer
latitude") in which transferability is satisfactory even under high
temperature and high humidity is wide. R.sup.0--SiO.sub.3/2 (1) (In
the formula (1), R.sup.0 represents an alkyl group having 1 or more
and 6 or less carbon atoms, or a phenyl group.)
The inventors of the present invention consider the reason that the
toner of the present invention has high transferability within a
wide transfer current range as described below.
The toner of the present invention contains the organosilicon
polymer having a partial structure represented by
R.sup.0--SiO.sub.3/2 (formula (1)) in the surface layer. In the
partial structure represented by the formula (1), one of the four
atomic valences of a Si atom is bonded to an organic group
represented by R.sup.0, and the other three atomic valences are
bonded to O atoms. The O atoms each form a state in which both two
atomic valences thereof are bonded to Si, that is, a siloxane bond
(Si--O--Si). When Si atoms and O atoms in the organosilicon polymer
as a whole are considered, the organosilicon polymer has three O
atoms per two Si atoms, and hence the Si atoms and the O atoms are
represented by --SiO.sub.3/2. That is, the organosilicon polymer
has a structure represented by the following formula (3).
##STR00001##
It is considered that the --SiO.sub.3/2 structure of the
organosilicon polymer has properties similar to those of silica
(SiO.sub.2) formed of a large number of siloxane structures. Thus,
it is considered that the toner of the present invention creates a
situation similar to that of the case where silica is added.
Meanwhile, it is considered that, through incorporation of R.sup.0,
there is some action different from that of silica.
Further, the toner particle of the present invention also has a
feature of including a surface layer derived from a resin particle
containing a resin having an ionic functional group and having a
pKa (acid dissociation constant) of 6.0 or more and 9.0 or less. It
is considered that the incorporation of both the resin having an
ionic functional group and the organosilicon polymer into the
surface layer is an important factor for expressing a wide transfer
latitude.
In a region of a low transfer current, a transfer electric field is
small relative to attraction force between a toner and a
photosensitive member, and hence a transfer residual toner is
generated. It is considered that the transfer latitude is widened
by decreasing the attraction force if possible. It is considered
that one component of the attraction force is non-electrostatic
adhesive force between the toner and the photosensitive member. It
has been made clear that the non-electrostatic adhesive force is
decreased when the organosilicon polymer and the resin having an
ionic functional group are allowed to coexist. In general, a toner
containing silica serving as an external additive on the surface of
a toner particle has a reducing effect on adhesive force. Under a
high-temperature and high-humidity environment, the adhesive force
is increased due to the influence of water. Meanwhile, the
organosilicon polymer of the present invention has a partial
structure represented by R.sup.0--SiO.sub.3/2 and contains R.sup.0
existing on the surface of a toner, and hence the density of oxygen
having high compatibility with water is smaller than that of
silica. Therefore, it is considered that there is a reducing effect
on an increase in adhesive force by moisture absorption. Further,
the resin having an ionic functional group and having a pKa of 6.0
or more and 9.0 or less has high hydrophobicity, and hence it is
similarly considered that there is a higher reducing effect on
adhesive force under a high-temperature and high-humidity
environment as compared to that of related-art toners.
Meanwhile, in a region of a high transfer current, discharge occurs
in a toner layer to generate a transfer residual toner. It is
considered that, under a high-temperature and high-humidity
environment, the charge quantity of a toner is low, and discharge
is liable to occur even in a region of a low transfer current, and
hence a transfer latitude becomes narrow. However, it is considered
that the resin having an ionic functional group of the present
invention has high hydrophobicity, and hence stable chargeability
can be expressed without being influenced by water, with the result
that a transfer latitude is widened. It is considered that, when
the resin that expresses the stable chargeability exists in the
surface layer, the effect is exhibited further strongly.
It is necessary that the toner particle according to the present
invention contain 5.0 number % or more of the silicon atoms (0.050
or more silicon atom) of the partial structure represented by the
formula (1) per 1.000 silicon atom contained in the organosilicon
polymer according to the present invention. That is, in a
.sup.29Si-NMR measurement of a tetrahydrofuran-insoluble matter of
the toner particle, the ratio of the peak area for the partial
structure represented by the formula (1) to the total peak area for
the organosilicon polymer is 5.0% or more. This means that 5.0% or
more of the silicon of the organosilicon polymer contained in the
toner particle correspond to the peak area for the partial
structure represented by --SiO.sub.3/2. A --SiO.sub.3/2 skeleton is
considered to be an element required for enhancing durability and
optimizing a charge density, and it is interpreted that 5.0% or
more of this structure needs to be incorporated. When the peak area
for the partial structure is less than 5.0%, the effect on
transferability is not exhibited easily through repeated use.
The --SiO.sub.3/2 indicates, for example, that three of the four
atomic valences of a Si atom are bonded to oxygen atoms, and the
oxygen atoms are further bonded to other Si atoms. When one of
those is SiOH, the partial structure of silicon thereof is
represented by R.sup.0--SiO.sub.2/2--OH. This structure is similar
to a disubstituted silicone resin typified by dimethyl silicone. It
is considered that, when the peak area for the structure of
--SiO.sub.3/2 is less than 5.0%, a resinous property becomes
dominant, and when the peak area for the structure of --SiO.sub.3/2
is 5.0% or more, a hard property, such as that of silica, starts
being expressed. That is assumed to be one factor for the
satisfactory effect on transferability through repeated use.
Meanwhile, it is considered that, in the case where a structure,
such as that of SiO.sub.2, is dominant, the hard property becomes
dominant, and there is an effect on transferability through
repeated use. However, in this case, it is considered that the
density of oxygen is high, and hence a reducing effect on adhesive
force is not obtained easily under a high-humidity environment. The
ratio of the peak area for the partial structure represented by the
formula (1) to the total peak area for the organosilicon polymer is
preferably 10.0% or more, more preferably 40.0% or more. It is
considered that, when the ratio falls within the range, the
structure of the organosilicon polymer is further strengthened, and
the oxygen density is optimized to improve charge stability.
Meanwhile, from the viewpoints of improvement of durability through
stabilization of the structure and charging stability, it is
preferred that the ratio of the peak area for the partial structure
represented by the formula (1) to the total peak area for the
organosilicon polymer be 100.0% or less. That is, it is most
preferred that the ratio be approximated to 100.0% by various
means. The ratio of the peak area for the partial structure
represented by the formula (1) to the total peak area for the
organosilicon polymer can be controlled by a reaction temperature
during formation of the partial structure of the formula (1) and a
pH during the reaction.
As described above, the toner of the present invention includes the
surface layer derived from the resin particle containing the resin
having an ionic functional group, the resin exhibiting stable
chargeability even under a high-temperature and high-humidity
environment, and further the surface layer contains the
organosilicon polymer that reduces adhesive force and has high
durability. The inventors of the present invention consider that,
by virtue of the effects of the surface layer, a wide transfer
latitude can be kept through repeated use.
Merely by causing the organosilicon polymer that exhibits a
reducing effect on adhesive force and an improving effect on
durability, and the resin having an ionic functional group that
exhibits stable chargeability even under a high-temperature and
high-humidity environment to each exist independently, the effects
of the present invention are not exhibited sufficiently. One of the
conditions for causing a wide transfer latitude to be exhibited
through endurance (repeated use) is that both the organosilicon
polymer and the resin having an ionic functional group exist in the
surface layer in an appropriate ratio.
As a method of analyzing existence amounts of the organosilicon
polymer and the resin having an ionic functional group, there are
given various methods, such as NMR and TOF-SIMS. In the present
invention, it has been made clear that there is a correlation
between a measured value of X-ray photoelectron spectroscopic
analysis and a transfer latitude, and hence X-ray photoelectron
spectroscopic analysis is effective analysis means.
In order to cause a wide transfer latitude to be exhibited, it is
preferred that, in X-ray photoelectron spectroscopic analysis of a
surface of the toner particle of the present invention, a ratio of
a silicon atom density dSi with respect to a total of 100.0 atomic
% of a carbon atom density dC, an oxygen atom density do, and the
silicon atom density dSi on the surface of the toner particle be
1.0 atomic % or more and 28.6 atomic % or less. The ratio is more
preferably 4.0 atomic % or more and 26.0 atomic % or less. When the
ratio falls within this range, the effects of the present invention
can be satisfactorily exhibited.
Main atoms of the toner particle that are generally considered are
carbon (C) and oxygen (O). In the present invention, when a silicon
(Si) atom exists in the surface of the toner particle, there exists
a portion in which an O atom is bonded to the Si atom. Then,
--SiO.sub.3/2 exists in an amount defined by the present invention.
Thus, it is considered that, when the dSi falls within the
above-mentioned range, the organosilicon polymer according to the
present invention exists in the surface of the toner particle, with
the result that the above-mentioned performance is improved. The
silicon atom density dSi on the surface of the toner particle can
be controlled by a content of the resin having an ionic functional
group.
The resin having an ionic functional group in the present invention
has a pKa of 6.0 or more and 9.0 or less. When the pKa (acid
dissociation constant) of the resin having an ionic functional
group is 6.0 or more and 9.0 or less, excellent charging
performance is exhibited under a high-humidity environment. This is
described below.
In general, a resin having a functional group, such as sulfonic
acid or carboxylic acid, is often used as the resin having an ionic
functional group. However, such resin adsorbs water easily, and the
adsorption may decrease a charge quantity under high temperature
and high humidity. However, when the pKa is 6.0 or more and 9.0 or
less, the hygroscopicity of the resin can be reduced to suppress
decrease in charge quantity under a high-humidity environment.
When the pKa is less than 6.0, a water adsorption amount is
increased, and chargeability is decreased under high humidity.
Further, when the pKa is more than 9.0, charging ability is low,
and sufficient chargeability may not be expressed. The pKa of the
resin having an ionic functional group is more preferably 7.0 or
more and 8.5 or less.
A method of determining a pKa is described later; the pKa can be
determined based on a neutralization titration result.
Any resin may be used as the resin having an ionic functional group
as long as the above-mentioned pKa is satisfied. For example, a
resin having a hydroxyl group bonded to an aromatic ring or a
carboxy group bonded to an aromatic ring can set the pKa within the
above-mentioned range. For example, a resin obtained by
polymerizing vinylsalicylic acid, 1-vinyl phthalate, vinyl
benzoate, and 1-vinylnatphthalene-2-carboxylic acid is
preferred.
Further, it is more preferred that the resin having an ionic
functional group comprises a polymer A having a monovalent group a
represented by the following formula (2) as a molecular
structure.
##STR00002## (In the formula (2), R.sup.1 represents a hydroxy
group, a carboxy group, an alkyl group having 1 or more and 18 or
less carbon atoms, or an alkoxy group having 1 or more and 18 or
less carbon atoms, R.sup.2 represents a hydrogen atom, a hydroxy
group, an alkyl group having 1 or more and 18 or less carbon atoms,
or an alkoxy group having 1 or more and 18 or less carbon atoms, g
represents an integer of 1 or more and 3 or less, h represents an
integer of 0 or more and 3 or less, and when h represents 2 or 3, h
R.sup.1's may be the same or different, and * represents a binding
site in a main chain structure of the polymer A.)
Examples of the alkyl group represented by R.sup.1 or R.sup.2
include a methyl group, an ethyl group, a propyl group, an
isopropyl group, a butyl group, an isobutyl group, a s-butyl group,
and a t-butyl group. Examples of the alkoxy group include a methoxy
group, an ethoxy group, and a propoxy group.
There is no particular limitation on a main chain structure of the
polymer A as long as the monovalent group a represented by the
formula (2) can be connected through the * portion. Examples of the
main chain structure include a vinyl-based polymer, a
polyester-based polymer, a polyamide-based polymer, a
polyurethane-based polymer, and a polyether-based polymer. There is
also given a hybrid-type polymer obtained by combining two or more
kinds of the polymers. Of those, the vinyl-based polymer is
preferred.
Further, it is preferred that the content of the monovalent group a
represented by the formula (2) contained in the polymer A be 50
.mu.mol/g or more and 1000 .mu.mol/g or less. When the content is
set to 50 .mu.mol/g or more, satisfactory chargeability and
durability can be exhibited. Further, when the content is set to
1,000 .mu.mol/g or less, charge-up can be suppressed.
A content of the monovalent group a represented by the formula (2)
in the polymer A can be determined by a method described below.
First, the polymer A is titrated by a method described later to
quantify an acid value of the polymer A, to thereby calculate an
amount of a carboxy group derived from the monovalent group a
represented by the formula (2) in the polymer A. Then, based on
this calculated amount, a content (.mu.mol/g) of the monovalent
group a represented by the formula (2) in the polymer A can be
calculated. When the polymer A has a carboxy group at a site except
the monovalent group a represented by the formula (2), an acid
value of a compound (for example, a polyester resin) immediately
before an addition reaction of the monovalent group a represented
by the formula (2) is measured in advance when the polymer A is
produced. An addition amount of the monovalent group a represented
by the formula (2) can be calculated based on a difference between
the acid value measured in advance and the acid value of the
polymer A after the addition reaction.
Further, a NMR measurement is performed to calculate a molar ratio
of each component based on a value of integral derived from a
characteristic chemical shift value of each monomer component, and
based on this calculated molar ratio, a content (.mu.mol/g) can be
calculated.
As means for causing the organosilicon polymer and the resin having
an ionic functional group to coexist, there are given various
methods. However, in order to cause the effects of the present
invention to be effectively exhibited, it is preferred that the
resin having an ionic functional group exist on the outermost
surface of a toner particle. Thus, it is preferred to employ a
procedure involving producing a toner base particle containing the
organosilicon polymer, and sticking the resin having an ionic
functional group to the toner base particle from outside.
Specific examples of the procedure include: a method involving
mixing a toner base particle and a resin particle containing the
resin having an ionic functional group in a dry process, and
sticking the resin particle to the toner base particle by
mechanical treatment; and a method involving dispersing the toner
base particle and the resin particle in an aqueous medium, and
heating the dispersion liquid or adding an aggregating agent to the
dispersion liquid. In the present invention, it is preferred that
the resin particle be stuck to the surface of the toner base
particle in the aqueous medium by heating for the following reason.
In the aqueous medium, the resin particles are dispersed under a
state of being charged, and hence the resin particles containing
the resin having an ionic functional group can be uniformly stuck
to the surface of the toner base particle without being aggregated.
Further, irregularities on the surface of a toner particle can be
increased in size, and hence the adhesive force of a toner can be
further decreased.
Any method may be used as a production method for a resin particle.
Resin particles produced by known methods, such as an emulsion
polymerization method, a soap-free emulsion polymerization method,
a phase inversion emulsification method, and a mechanical
emulsification method, can be used. Of those production methods,
the phase inversion emulsification method is preferred because an
emulsifier and a dispersion stabilizer are not required, and a
resin particle having a smaller particle diameter can be obtained
easily.
In the phase inversion emulsification method, a resin having
self-dispersibility or a resin capable of expressing
self-dispersibility through neutralization is used. Herein,
self-dispersibility in an aqueous medium is exhibited in a resin
having a hydrophilic group in a molecule. Specifically,
satisfactory self-dispersibility is exhibited in a resin having a
polyether group or an ionic functional group.
For production of the resin particle of the present invention, a
resin having an ionic functional group, which expresses
self-emulsifiability through neutralization, is used. Specifically,
a resin having an ionic functional group and having a pKa (acid
dissociation constant) of 6.0 or more and 9.0 or less is used.
When the ionic functional group in the above-mentioned resin is
neutralized, hydrophilicity is increased and self-dispersion in an
aqueous medium is realized. When the resin is dissolved in an
organic solvent, and a neutralizing agent is added to the solution,
followed by mixing with an aqueous medium with stirring, the
solution of the resin is subjected to phase inversion
emulsification to generate fine particles. The organic solvent is
removed by a method, such as heating or reduction in pressure,
after the phase inversion emulsification. Thus, according to the
phase inversion emulsification method, a stable aqueous dispersion
of resin particles can be obtained substantially without using an
emulsifier or a dispersion stabilizer.
In the present invention, it is preferred that, regarding the
average particle diameter of the resin particle, a median diameter
(D50) on a volume basis, which is determined by a particle size
distribution measurement according to a laser scattering method,
fall within the range of 5 nm or more and 200 nm or less. More
preferably, the median diameter (D50) on a volume basis falls
within the range of 20 nm or more and 130 nm or less. When the
median diameter (D50) on a volume basis is 5 nm or more, sufficient
durability is obtained. Further, when the median diameter (D50) on
a volume basis is 200 nm or less, the resin particles can be stuck
to the toner base particle more uniformly.
The surface layer in which the organosilicon polymer and the resin
having an ionic functional group exist can be defined by observing
a cross-section of the toner particle through use of a transmission
electron microscope (TEM), and the detail thereof is described
later. It is preferred that an average thickness Dav. of the
surface layer be 5.0 nm or more. By virtue of the surface layer, an
enlarging effect on a fogging latitude is obtained, and in
addition, the toner particle can be protected from toner
degradation factors through repeated use, such as rubbing and
pressure. Thus, a wide transfer latitude can be kept further. The
average thickness Dav. is more preferably 10.0 nm or more.
Meanwhile, from the viewpoint of low-temperature fixability, the
average thickness Dav. is preferably 300.0 nm or less, more
preferably 150.0 nm or less.
Further, in the present invention, a ratio of the number of line
segments in which the thickness of the surface layer is 2.5 nm or
less (hereinafter sometimes referred to as "ratio of a thickness of
2.5 nm or less of the surface layer") is preferably 20.0% or less,
more preferably 10.0% or less.
Further, when a ratio of the number of line segments in which the
thickness of the surface layer of a toner containing the
organosilicon polymer is 2.5 nm or less is 20.0% or less, a toner
having excellent durability even in a wide environment and severe
usage can be obtained. It is considered that, when the
above-mentioned conditions are satisfied, high durability by the
--SiO.sub.3/2 structure is expressed strongly, and durable
sustainability of a transfer latitude is significantly improved
along with an action with the resin having an ionic functional
group.
The average thickness Dav. of the surface layer and the ratio of a
thickness of 2.5 nm or less of the surface layer can be controlled
by a production method for a toner particle during formation of an
organosilicon polymer, hydrolysis during formation of the
organosilicon polymer, and a reaction temperature, a reaction time,
a reaction solvent, and a pH during polymerization. The average
thickness Dav. of the surface layer and the ratio of a thickness of
2.5 nm or less of the surface layer can also be controlled by the
content of the organosilicon polymer. Further, the average
thickness Dav. of the surface layer and the ratio of a thickness of
2.5 nm or less of the surface layer can be controlled by the number
of addition parts of the resin having an ionic functional group,
and the particle diameter of the resin particle.
In the present invention, it is more preferred that R.sup.0 in the
formula (1), which is a partial structure of the organosilicon
polymer, represent a methyl group or an ethyl group. With this, the
fogging latitude-enlarging effect in the present invention can be
exhibited more strongly. The inventors of the present invention
assume the reason for the foregoing as follows: the density of
oxygen is in a state preferred for exhibiting the effect.
It is preferred that the organosilicon polymer to be used in the
present invention be a polymer of an organosilicon compound having
a structure represented by the following formula (4).
##STR00003## (In the formula (4), R.sup.3 represents a saturated
hydrocarbon group or an aryl group, and R.sup.4, R.sup.5, and
R.sup.6 each independently represent a halogen atom, a hydroxy
group, an acetoxy group, or an alkoxy group.)
Through hydrolysis, addition polymerization, and condensation
polymerization of the R.sup.4, R.sup.5, and R.sup.6, a
--Si--O--Si-- structure is obtained easily, and conditions can be
controlled easily. It is preferred that the R.sup.4, R.sup.5, and
R.sup.6 each represent an alkoxy group from the viewpoints of
controllability of polymerization conditions and ease of formation
of a siloxane structure. From the viewpoints of a precipitation
property and a covering property of the organosilicon polymer with
respect to the surface of the toner particle, it is more preferred
that the R.sup.4, R.sup.5, and R.sup.6 each represent a methoxy
group or an ethoxy group. The hydrolysis, addition polymerization,
and condensation polymerization of the R.sup.4, R.sup.5, and
R.sup.6 can be controlled based on a reaction temperature, a
reaction time, a reaction solvent, and a pH.
Further, as the saturated hydrocarbon group of the R.sup.3, there
is given an alkyl group having 1 to 6 carbon atoms. The saturated
hydrocarbon group is more preferably a methyl group, an ethyl
group, or a butyl group, still more preferably a methyl group or an
ethyl group. As the aryl group of the R.sup.3, a phenyl group is
preferred. For example, when an organosilicon compound in which the
R.sup.3 represents a methyl group or an ethyl group is used,
R.sup.0 in the formula (1) can be a methyl group or an ethyl
group.
Specific examples of the organosilicon compound for producing the
organosilicon polymer in the present invention include
methyltrimethoxysilane, methyltriethoxysilane,
methyltrichlorosilane, ethyltrimethoxysilane, ethyltriethoxysilane,
ethyltrichlorosilane, ethyltriacetoxysilane,
propyltrimethoxysilane, propyltriethoxysilane,
propyltrichlorosilane, butyltrimethoxysilane, butyltriethoxysilane,
butyltrichlorosilane, butylmethoxydichlorosilane,
butylethoxydichlorosilane, hexyltrimethoxysilane,
hexyltriethoxysilane, phenyltrimethoxysilane, and
phenyltriethoxysilane. One kind of those organosilicon compounds
may be used alone, or two or more kinds thereof may be used in
combination.
In general, it is known that, in a sol-gel reaction, the bonding
state of a siloxane bond to be generated varies depending on the
acidity of a reaction medium. Specifically, when the medium is
acidic, a hydrogen ion is electrophilically added to oxygen of one
reaction group (for example, an alkoxy group (--OR group)). Then,
an oxygen atom in a water molecule is coordinated to a silicon atom
to become a hydrosilyl group through a substitution reaction. When
water exists sufficiently, one H.sup.+ attacks one oxygen of the
reaction group (for example, an alkoxy group (--OR group)).
Therefore, when the content of H.sup.+ in the medium is small, the
substitution reaction to a hydroxy group becomes slow. Thus, a
polycondensation reaction occurs before all the reaction groups
bonded to silane are subjected to hydrolysis, with the result that
a one-dimensional linear polymer or a two-dimensional polymer is
generated relatively easily.
Meanwhile, when the medium is alkaline, a hydroxide ion is added to
silicon to form a five-coordinated intermediate. Therefore, all the
reaction groups (for example, alkoxy groups (--OR groups)) are
easily detached to be easily substituted by a silanol group. In
particular, when a silicon compound having three or more reaction
groups in the same silane is used, hydrolysis and polycondensation
occur three-dimensionally, to thereby form an organosilicon polymer
containing a large number of three-dimensional crosslinking bonds.
Further, the reaction is finished within a short period of
time.
Thus, in order to form an organosilicon polymer, it is preferred
that the sol-gel reaction proceed under an alkaline state. When an
organosilicon polymer is produced in an aqueous medium,
specifically, it is preferred that the reaction proceed under the
conditions of a pH of 8.0 or more, a reaction temperature of
90.degree. C. or more, and a reaction time of 5 hours or more. With
this, an organosilicon polymer having higher strength and being
excellent in durability can be formed.
Next, a method of producing the toner particle of the present
invention is described. The following resins can be used as the
other additives within a range not influencing the effects of the
present invention: homopolymers of styrene and substituted
styrenes, such as polystyrene and polyvinyltoluene; styrene-based
copolymers, such as a styrene-propylene copolymer, a
styrene-vinyltoluene copolymer, a styrene-vinylnaphthalene
copolymer, a styrene-methyl acrylate copolymer, a styrene-ethyl
acrylate copolymer, a styrene-butyl acrylate copolymer, a
styrene-octyl acrylate copolymer, a styrene-dimethylaminoethyl
acrylate copolymer, a styrene-methyl methacrylate copolymer, a
styrene-ethyl methacrylate copolymer, a styrene-butyl methacrylate
copolymer, a styrene-dimethylaminoethyl methacrylate copolymer, a
styrene-vinyl methyl ether copolymer, a styrene-vinyl ethyl ether
copolymer, a styrene-vinyl methyl ketone copolymer, a
styrene-butadiene copolymer, a styrene-isoprene copolymer, a
styrene-maleic acid copolymer, and a styrene-maleate copolymer; and
polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate,
polyethylene, polypropylene, polyvinyl butyral, a silicone resin, a
polyester resin, a polyamide resin, an epoxy resin, a polyacrylic
resin, rosin, modified rosin, a terpene resin, a phenol resin, an
aliphatic or alicyclic hydrocarbon resin, and an aromatic petroleum
resin. One kind of those resins may be used alone, or two or more
kinds thereof may be used as a mixture.
Now, a specific method of producing the toner of the present
invention is described, but the present invention is not limited
thereto.
As a first production method, there is provided a method of
obtaining a toner particle by a suspension polymerization method.
More specifically, the method includes: a step (i) of forming a
particle of a polymerizable monomer composition, which contains a
polymerizable monomer, a colorant, and an organosilicon compound
represented by the formula (4), in an aqueous medium; a step (ii)
of polymerizing at least a part of the polymerizable monomer and
the organosilicon compound contained in the particle of the
polymerizable monomer composition to obtain a dispersion liquid of
a polymer particle (toner base particle); and a step (iii) of
adding a resin particle containing the resin having an ionic
functional group to the dispersion liquid of the polymer
particle.
The above-mentioned method is the most preferred production method
because a layer containing the organosilicon polymer is formed on a
surface, and the resin having an ionic functional group can be
scattered uniformly on the outermost surface.
Further, in the step (ii) of the above-mentioned production method,
the following method is also used, which involves taking out the
organosilicon polymer as powder after the polymer has been formed
into the surface layer and sticking the resin particle containing
the resin having an ionic functional group to the surface of the
powder in a dry process.
As a second production method, there is provided a method involving
obtaining a toner base particle, and then forming a surface layer
of an organosilicon polymer and the resin having an ionic
functional group in an aqueous medium. The toner base particle may
be obtained by melting and kneading a binder resin and a colorant,
and pulverizing the resultant, or may be obtained by aggregating
binder resin particles and colorant particles in an aqueous medium,
and associating the aggregate. Alternatively, the toner base
particle may be obtained by suspending and granulating an organic
phase dispersion liquid, which is produced by dissolving a binder
resin and a colorant in an organic solvent, in an aqueous medium,
and thereafter removing the organic solvent.
As a third production method, there is provided a method involving:
subjecting an organic phase dispersion liquid, which is produced by
dissolving a binder resin, an organosilicon compound, and a
colorant in an organic solvent, to suspension, granulation, and
polymerization in an aqueous medium; removing the organic solvent
to obtain a toner base particle; and then adding the resin particle
containing the resin having an ionic functional group to the toner
base particle. Also in this method, the organosilicon compound is
polymerized in the vicinity of the surface of a toner particle
under a state of being precipitated on the surface of the toner,
and the resin having an ionic functional group exists on an outer
side of the organosilicon polymer.
As a fourth production method, there is provided a method involving
aggregating a binder resin particle, a colorant particle, an
organosilicon compound-containing particle in a sol or gel state,
and the resin particle containing the resin having an ionic
functional group in an aqueous medium, and associating the
aggregate, to thereby form a toner particle.
As a fifth production method, there is provided a method involving
spraying a solvent containing the organosilicon compound and the
resin particle containing the resin having an ionic functional
group onto the surface of a toner base particle by a spray-dry
method, and polymerizing or drying the surface by hot wind and
cooling, to thereby form a surface layer containing the
organosilicon polymer and the resin having an ionic functional
group. The toner base particle may be obtained by melting and
kneading a binder resin and a colorant, and pulverizing the
resultant, or may be obtained by aggregating binder resin particles
and colorant particles in an aqueous medium, and associating the
aggregate. Alternatively, the toner base particle may be obtained
by suspending and granulating an organic phase dispersion liquid,
which is produced by dissolving a binder resin and a colorant in an
organic solvent, in an aqueous medium, and thereafter removing the
organic solvent.
The method involving sticking the resin particle containing the
resin having an ionic functional group and having a pKa of 6.0 or
more and 9.0 or less to the toner base particle in the aqueous
medium to be used in the present invention is described.
In the step (sticking step) of sticking the resin particle
containing the resin having an ionic functional group to the
surface of the toner base particle in the aqueous medium, it is
preferred that the pH (hydrogen ion concentration) of the aqueous
medium be (pKa of the resin particle-2.0) or more.
The resin to be used in the present invention has a pKa (acid
dissociation constant) of 6.0 or more and 9.0 or less, and hence
the dissociation of an ionic functional group of the resin depends
on the pH of the aqueous medium. When the pH of the aqueous medium
is low, and few ionic functional groups dissociate, it is
considered that there are many portions on the surface of the resin
particle, which are not charged, and resin particles are easily
brought into contact with each other and are stuck to the surface
of a toner base particle under a state of being aggregated. In this
sticking state, owing to the contact between toner particles or
between a toner and a charging member, an aggregate of the resin
particles is easily detached from the toner base particle, with
result that charging stability is contrarily decreased. Further,
the detached aggregate itself of the resin particles may cause
contamination of members, and the contamination decreases
durability. In the above-mentioned pH region, the aggregation of
resin particles is suppressed, and the resin particles are
uniformly and strongly stuck to a toner base particle, and hence
excellent charging stability of the resin particles can be kept for
a long period of time. Meanwhile, when the pH of the aqueous medium
is less than (pKa of the resin-2.0), the dissociation of an ionic
functional group of a resin hardly occurs, and resin particles are
stuck to the surface of a toner base particle under a state of
being aggregated. The pH of the aqueous medium is preferably at
least the pKa of the resin. Further, it is preferred that the pH of
the aqueous medium be (pKa of the resin+4.0) or less in order to
suppress excessive dissociation of an ionic functional group.
As the sticking method for a resin particle, known procedures can
be applied as long as the pH of the aqueous medium is adjusted to
(pKa of the resin-2.0) or more. For example, a resin particle may
be added to a dispersion liquid of a toner base particle and then
buried in the toner base particle with mechanical force of impact,
or the resin particle may be stuck to the toner base particle by
heating the aqueous medium. Alternatively, the resin particle may
be stuck to the toner base particle by adding an aggregating agent,
or the above-mentioned procedures may be combined. In any case, it
is preferred that the aqueous medium be stirred.
From the viewpoint of strongly sticking the resin particle to the
toner base particle, a procedure for heating the aqueous medium to
at least a glass transition temperature of the toner base particle
is more preferred. Through setting of the aqueous medium to the
above-mentioned temperature, the toner base particle is softened
and is immobilized when the resin particle is brought into contact
with the toner base particle.
Further, in the sticking step, it is preferred that a zeta
potential of the toner base particle be larger by 10 mV or more
than a zeta potential of the resin particle. When the zeta
potential of the toner base particle is larger by 10 mV or more
than the zeta potential of the resin particle, the resin particle
is electrostatically stuck to the toner base particle. Therefore,
sticking can be performed within a short period of time, and
variation between toner particles can be suppressed.
The zeta potential of the toner base particle can be controlled
through use of the above-mentioned dispersion stabilizer.
Specifically, the zeta potential of the toner base particle can be
controlled by the kind and amount of, and an adhesion method for,
the dispersion stabilizer adhering to the surface of the toner base
particle.
After the resin particle is stuck to the surface of the toner base
particle, the resultant is subjected to filtration, washing, and
drying by known methods to provide a toner particle. When an
inorganic dispersion stabilizer is used, it is preferred that the
dispersion stabilizer be dissolved in an acid or a base and then
removed.
As the preferred aqueous medium in the present invention, there are
given: water, alcohols, such as methanol, ethanol, and propanol,
and mixed solvents thereof.
Preferred examples of the polymerizable monomer in the suspension
polymerization method may include the following vinyl-based
polymerizable monomers: styrene; styrene derivatives, such as
.alpha.-methylstyrene, .beta.-methylstyrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene,
p-n-butylstyrene, p-tert-butylstyrene, p-n-hexylstyrene,
p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene,
p-n-dodecylstyrene, p-methoxystyrene, and p-phenylstyrene; acrylic
polymerizable monomers, such as methyl acrylate, ethyl acrylate,
n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl
acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate,
2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate,
cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl
acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl
acrylate, and 2-benzoyloxy ethyl acrylate; methacrylic
polymerizable monomers, such as methyl methacrylate, ethyl
methacrylate, n-propyl methacrylate, iso-propyl methacrylate,
n-butyl methacrylate, iso-butyl methacrylate, tert-butyl
methacrylate, n-amyl methacrylate, n-hexyl methacrylate,
2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl
methacrylate, diethyl phosphate ethyl methacrylate, and dibutyl
phosphate ethyl methacrylate; methylene aliphatic monocarboxylic
acid esters; vinyl esters, such as vinyl acetate, vinyl propionate,
vinyl benzoate, vinyl butyrate, vinyl benzoate, and vinyl formate;
vinyl ethers, such as vinyl methyl ether, vinyl ethyl ether, and
vinyl isobutyl ether; and vinyl methyl ketone, vinyl hexyl ketone,
and vinyl isopropyl ketone.
In addition, as a polymerization initiator to be used in the
polymerization, the following polymerization initiators are given:
azo-based or diazo-based polymerization initiators, such as
2,2'-azobis-(2,4-divaleronitrile), 2,2'-azobisisobutyronitrile,
1,1'-azobis(cyclohexane-1-carbonitrile),
2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, and
azobisisobutyronitrile; and peroxide-based polymerization
initiators, such as benzoyl peroxide, methyl ethyl ketone peroxide,
diisopropyl oxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl
peroxide, and lauroyl peroxide. Any such polymerization initiator
is preferably added in an amount of 0.5 mass % or more and 30.0
mass % or less with respect to the polymerizable monomer. One kind
of those polymerization initiators may be used alone, or two or
more kinds thereof may be used in combination.
Further, in order to control the molecular weight of the binder
resin forming the toner particle, a chain transfer agent may be
added in the polymerization. The addition amount thereof is
preferably 0.001 mass % or more and 15.0 mass % or less of the
polymerizable monomer.
Meanwhile, in order to control the molecular weight of the binder
resin forming the toner particle, a crosslinking agent may be added
in the polymerization. As a crosslinkable monomer, there are given:
divinylbenzene, bis(4-acryloxypolyethoxyphenyl)propane, ethylene
glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol
diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate,
neopentyl glycol diacrylate, diethylene glycol diacrylate,
triethylene glycol diacrylate, tetraethylene glycol diacrylate,
diacrylates of polyethylene glycols #200, #400, and #600,
dipropylene glycol diacrylate, polypropylene glycol diacrylate, a
polyester-type diacrylate (MANDA manufactured by Nippon Kayaku Co.,
Ltd.), and monomers obtained by changing the above-mentioned
acrylates to methacrylates.
As a polyfunctional crosslinkable monomer, there are given:
pentaerythritol triacrylate, trimethylolethane triacrylate,
trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate,
oligoester acrylate, and methacrylates thereof,
2,2-bis(4-methacryloxy polyethoxyphenyl)propane, diallyl phthalate,
triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate,
and diallyl chlorendate. The addition amount thereof is preferably
0.001 mass % or more and 15.0 mass % or less with respect to the
polymerizable monomer.
When the medium to be used in the suspension polymerization is an
aqueous medium, the following may be used as a dispersion
stabilizer for a particle of the polymerizable monomer composition:
tricalcium phosphate, magnesium phosphate, zinc phosphate, aluminum
phosphate, calcium carbonate, magnesium carbonate, calcium
hydroxide, magnesium hydroxide, aluminum hydroxide, calcium
metasilicate, calcium sulfate, barium sulfate, bentonite, silica,
and alumina. In addition, as an organic dispersant, there are given
polyvinyl alcohol, gelatin, methylcellulose,
methylhydroxypropylcellulose, ethylcellulose,
carboxymethylcellulose sodium salt, and starch.
In addition, a commercially available nonionic, anionic, or
cationic surfactant can also be utilized. Examples of the
surfactant include sodium dodecyl sulfate, sodium tetradecyl
sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium
oleate, sodium laurate, and potassium stearate.
There is no particular limitation on the colorant to be used in the
toner of the present invention, and the following known colorants
may be used.
Used as a yellow pigment is yellow iron oxide, naples yellow, a
condensed azo compound, such as naphthol yellow S, hansa yellow G,
hansa yellow 10G, benzidine yellow G, benzidine yellow GR, a
quinoline yellow lake, permanent yellow NCG, or tartrazine lake, an
isoindoline compound, an anthraquinone compound, an azo metal
complex, a methine compound, or an allyl amide compound. Specific
examples thereof include C.I. Pigment Yellow 12, 13, 14, 15, 17,
62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 155, 168, and
180.
As an orange pigment, there are given permanent orange GTR,
pyrazolone orange, Vulcan orange, benzidine orange G, indanthrene
brilliant orange RK, and indanthrene brilliant orange GK.
As a red pigment, there are given colcothar, condensed azo
compounds, such as permanent red 4R, lithol red, pyrazolone red,
watching red calcium salt, lake red C, lake red D, brilliant
carmine 6B, brilliant carmine 3B, eosine lake, rhodamine lake B,
and alizarin lake, a diketopyrrolopyrrol compound, anthraquinone, a
quinacridone compound, a basic dye lake compound, a naphthol
compound, a benzimidazolone compound, a thioindigo compound, and a
perylene compound. Specific examples thereof include C.I. Pigment
Red 2, 3, 5, 6, 7, 23, 48:2, 48:3, 48:4, 57:1, 81:1, 122, 144, 146,
166, 169, 177, 184, 185, 202, 206, 220, 221, and 254.
As a blue pigment, there are given alkali blue lake, Victoria blue
lake, copper phthalocyanine compounds, such as phthalocyanine blue,
metal-free phthalocyanine blue, a partial chloride of
phthalocyanine blue, fast sky blue, and indanthrene blue BG, and
derivatives thereof, an anthraquinone compound, and a basic dye
lake compound. Specific examples thereof include C.I. Pigment Blue
1, 7, 15, 15:1, 15:2, 15:3, 15:4, 60, 62, and 66.
As a violet pigment, there are given fast violet B and methyl
violet lake.
As a green pigment, there are given Pigment Green B, malachite
green lake, and final yellow green G. As a white pigment, there are
given zinc white, titanium oxide, antimony white, and zinc
sulfide.
As a black pigment, there are given carbon black, aniline black,
non-magnetic ferrite, magnetite, and a pigment toned to black with
the above-mentioned yellow, red, and blue colorants. One kind of
those colorants may be used alone, or two or more kinds thereof may
be used as a mixture, and in the state of a solid solution.
The content of the colorant is preferably 3.0 parts by mass or more
and 15.0 parts by mass or less with respect to 100 parts by mass of
the binder resin or the polymerizable monomer.
A charge control agent except the resin having an ionic functional
group and having a specific pKa may be used in the toner of the
present invention during production thereof, and known charge
control agents can be used. The addition amount of any such charge
control agent is preferably 0.01 part by mass or more and 10.0
parts by mass or less with respect to 100 parts by mass of the
binder resin or the polymerizable monomer.
In the toner of the present invention, various organic or inorganic
fine powders may be externally added to the toner particle as
necessary. It is preferred that any such organic or inorganic fine
powder have a particle diameter of 1/10 or less of the
weight-average particle diameter of the toner particle from the
viewpoint of durability at time of addition to the toner particle.
For example, the following fine powder is used as the organic or
inorganic fine powder. (1) Fluidity imparting agents: silica,
alumina, titanium oxide, carbon black, and carbon fluoride. (2)
Abrasives: metal oxides (such as strontium titanate, cerium oxide,
alumina, magnesium oxide, and chromium oxide), nitrides (such as
silicon nitride), carbides (such as silicon carbide), and metal
salts (such as calcium sulfate, barium sulfate, and calcium
carbonate). (3) Lubricants: fluorine-based resin powders (such as
vinylidene fluoride and polytetrafluoroethylene) and fatty acid
metal salts (such as zinc stearate and calcium stearate). (4)
Charge controllable particles: metal oxides (such as tin oxide,
titanium oxide, zinc oxide, silica, and alumina) and carbon
black.
The surface of the toner particle may be treated with the organic
or inorganic fine powder in order to improve the flowability of the
toner and to uniformize the charging of the toner particle. As a
treatment agent for hydrophobic treatment of the organic or
inorganic fine powder, there are given an unmodified silicone
varnish, various modified silicone varnishes, an unmodified
silicone oil, various modified silicone oils, a silane compound, a
silane coupling agent, other organosilicon compounds, and an
organotitanium compound. One kind of those treatment agents may be
used alone, or two or more kinds thereof may be used in
combination.
Various measurement methods related to the present invention are
described below.
<NMR Measurement Method (Confirmation of Partial Structure
Represented by Formula (1))>
The partial structure represented by the formula (1) in the
organosilicon polymer contained in the toner particle was confirmed
by the following solid NMR measurement. The measurement conditions
and sample preparation method are as described below.
"Measurement Conditions" Apparatus: JNM-EX400 manufactured by JEOL
Ltd. Probe: 6 mm CP/MAS probe Measurement temperature: room
temperature Reference substance: polydimethylsilane (PDMS)
(external reference: -34.0 ppm) Measured nucleus: .sup.29Si
(resonance frequency: 79.30 MHz) Pulse mode: CP/MAS Pulse width:
6.4 .mu.sec Repetition time: ACQTM=25.6 msec, PD=15.0 sec Data
points: POINT=4,096, SAMPO=1,024 Contact time: 5 msec Spectrum
width: 40 kHz Sample spinning rate: 6 kHz Number of scans: 2,000
scans Sample: 200 mg of a measurement sample (its preparation
method is described below) is loaded into a sample tube having a
diameter of 6 mm.
Preparation of a measurement sample: 10.0 g of toner particles are
weighed and loaded into a cylindrical paper filter (No. 86R
manufactured by Toyo Roshi Kaisha, Ltd.). The resultant is
subjected to extraction with a Soxhlet extractor for 20 hours
through use of 200 ml of tetrahydrofuran (THF) as a solvent. The
residue in the cylindrical paper filter is dried in a vacuum at
40.degree. C. for several hours, and the resultant is defined as a
THF-insoluble matter of the toner particle for NMR measurement.
After the measurement, a plurality of silane components having
different substituents and bonding groups of the toner particle are
subjected to peak separation by curve fitting into the following Q1
structure, Q2 structure, Q3 structure, and Q4 structure, and mol %
of each component is calculated from an area ratio of the
peaks.
Software EXcalibur for Windows (trademark) version 4.2 (EX series)
for JNM-EX400 manufactured by JEOL Ltd. was used for the curve
fitting. Measurement data is opened by clicking "1D Pro" in menu
icons.
Next, "Curve fitting function" was selected from "Command" of a
menu bar, and then curve fitting was performed. An example thereof
is shown in FIG. 2. Peak separation was performed so that a peak of
a synthesis peak difference (a) that was a difference between a
synthesis peak (b) and a measurement result (d) became minimum.
An area for the Q1 structure, an area for the Q2 structure, an area
for the Q3 structure, and an area for the Q4 structure are
determined, and SQ1, SQ2, SQ3, and SQ4 are determined by the
following formulae. Q1 structure:
(R.sup.7)(R.sup.8)(R.sup.9)SiO.sub.1/2 Formula (5) Q2 structure:
(R.sup.10)(R.sup.11)Si(O.sub.1/2).sub.2 Formula (6) Q3 structure:
R.sup.12Si(O.sub.1/2).sub.3 Formula (7) Q4 structure:
Si(O.sub.1/2).sub.4 Formula (8)
##STR00004## (In the formulae (5), (6), and (7), R.sup.7, R.sup.8,
R.sup.9, R.sup.10, R.sup.11, and R.sup.12 each represent an organic
group bonded to silicon, a halogen atom, a hydroxy group, or an
alkoxy group.)
In the present invention, a silane monomer is identified by a
chemical shift value, and in the .sup.29Si-NMR measurement of the
toner particle, from a total peak area, a total of the area for the
Q1 structure, the area for the Q2 structure, the area for the Q3
structure, and the area for the Q4 structure is defined as a total
peak area for the organosilicon polymer. SQ1+SQ2+SQ3+SQ4=1.000
SQ1={area for Q1 structure/(area for Q1 structure+area for Q2
structure+area for Q3 structure+area for Q4 structure)} SQ2={area
for Q2 structure/(area for Q1 structure+area for Q2 structure+area
for Q3 structure+area for Q4 structure)} SQ3={area for Q3
structure/(area for Q1 structure+area for Q2 structure+area for Q3
structure+area for Q4 structure)} SQ4={area for Q4 structure/(area
for Q1 structure+area for Q2 structure+area for Q3 structure+area
for Q4 structure)}
In the present invention, the ratio of the peak area for the
partial structure represented by the following formula (1) to the
total peak area for the organosilicon polymer is 5.0% or more. That
is, in this measurement method, the value indicating the
--SiO.sub.3/2 structure is the SQ3. This value is 0.050 or more.
R.sup.0--SiO.sub.2/3 (1)
Chemical shift values of silicon in the Q1 structure, the Q2
structure, the Q3 structure, and the Q4 structure are shown below.
An example of the Q1 structure
(R.sup.7.dbd.R.sup.8.dbd.--OC.sub.2H.sub.5,
R.sup.9.dbd.--CH.sub.3): -47 ppm An example of the Q2 structure
(R.sup.10.dbd.--OC.sub.2H.sub.5, R.sup.11.dbd.--CH.sub.3): -56 ppm
An example of the Q3 structure (R.sup.12.dbd.--CH.sub.3): -65
ppm
Further, a chemical shift value of silicon when the Q4 structure is
present is shown below. Q4 structure: -108 ppm
[Confirmation Method for Partial Structure Represented by Formula
(1)]
The presence/absence of an organic group represented by R.sup.0 in
the formula (1) is confirmed by .sup.13C-NMR. Further, the detailed
structure of the formula (1) is confirmed by .sup.1H-NMR,
.sup.13C-NMR, and .sup.29Si-NMR. An apparatus and measurement
conditions used are as described below.
"Measurement Conditions" Apparatus: AVANCE III 500 manufactured by
Bruker Corporation Probe: 4 mm MAS BB/1H Measurement temperature:
room temperature Sample spinning rate: 6 kHz Sample: 150 mg of a
measurement sample (THF-insoluble matter of the toner particle for
the NMR measurement) is loaded into a sample tube having a diameter
of 4 mm.
The presence/absence of the organic group represented by R.sup.0 in
the formula (1) was confirmed by the method. The structure
represented by the formula (1) is "present" when a signal is
confirmed.
".sup.13C-NMR (Solid) Measurement Conditions" Measured nucleus
frequency: 125.77 MHz Reference substance: glycine (external
standard: 176.03 ppm) Measurement width: 37.88 kHz Measurement
method: CP/MAS Contact time: 1.75 ms Repetition time: 4 s Number of
scans: 2,048 scans LB value: 50 Hz
In the present invention, when the organic fine powder or the
inorganic fine powder is externally added to the toner, toner
particles are obtained through the removal of the organic fine
powder or the inorganic fine powder by the following method.
160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) is
added to 100 mL of ion-exchanged water and dissolved through use of
a water bath, to thereby prepare a sucrose concentrated solution.
31 g of the sucrose concentrated solution and 6 mL of Contaminon N
(10 mass % aqueous solution of a neutral detergent for washing a
precision measuring device formed of a nonionic surfactant, an
anionic surfactant, and an organic builder and having a pH of 7,
manufactured by Wako Pure Chemical Industries, Ltd.) are loaded
into a centrifugation tube, to thereby produce a dispersion liquid.
1.0 g of the toner is added to the dispersion liquid, and a toner
lump is broken with a spatula or the like.
The centrifugation tube is shaken with a shaker at 350 strokes per
min (spm) for 20 minutes. After the shaking, the solution is
transferred into a glass tube for a swing rotor (50 mL) and
subjected to centrifugation with a centrifugal separator under the
conditions of 3,500 rpm and 30 minutes. With this operation, the
solution is separated into toner particle and external additives
detached from the toner particle. It is confirmed visually that the
toner and the aqueous solution have been sufficiently separated,
and the toner separated into the uppermost layer is collected with
a spatula or the like. The collected toner is filtered with a
vacuum filter and then dried with a drier for 1 hour or more, to
thereby provide toner particles. A required amount is obtained by
performing this operation a plurality of times.
<Method of Measuring Average Thickness Dav. Of Surface Layer of
Toner Particle, and Ratio of Thickness of 2.5 nm or Less of Surface
Layer, to be Measured by Observation of Cross-Section of Toner
Particle Through Use of Transmission Electron Microscope
(TEM)>
In the present invention, a cross-section of a toner particle is
observed by the following method.
A specific method of observing a cross-section of a toner particle
is as described below. Toner particles are sufficiently dispersed
in an epoxy resin that is curable at normal temperature, and then
the resultant is cured under an atmosphere of 40.degree. C. for 2
days. A flake-like sample is cut out from the obtained cured
product through use of a microtome provided with diamond teeth. The
sample is magnified at a magnification of from 10,000 times to
100,000 times with a transmission electron microscope (TEM)
(electron microscope Tecnai TF20XT manufactured by FEI Company),
and cross-sections of the toner particles are observed.
In the present invention, the cross-sections are confirmed through
use of: a difference in atomic weight between atoms in a resin and
an organosilicon compound to be used; and the fact that contrast is
increased when an atomic weight is large. Further, in order to
provide contrast between materials, a ruthenium tetroxide staining
method and an osmium tetroxide staining method are used.
A particle used in the measurement is determined as described
below. A circle-equivalent diameter Dtem of a toner particle is
determined based on its cross-section obtained from the TEM image,
and when a value thereof falls within a range of .+-.10% of the
weight-average particle diameter of the toner particle determined
by a method described later, that particle is defined as the
particle used in the measurement.
A light field image of a cross-section of a toner particle is
acquired at an acceleration voltage of 200 kV through use of an
electron microscope Tecnai TF20XT manufactured by FEI Company as
described above. Next, an EF mapping image of a Si--K end (99 eV)
is acquired by a Three Window method through use of an EELS
detector GIF Tridiem manufactured by Gatan, Inc. to confirm that an
organosilicon polymer exists in a surface layer.
Then, a cross-section of one toner particle whose circle-equivalent
diameter Dtem falls within a range of .+-.10% of the weight-average
particle diameter of the toner particle is equally divided into 16
sections, with an intersection between a long axis L that is the
maximum diameter of the cross-section of the toner particle and an
axis L90 that passes through a midpoint of the long axis L and is
perpendicular thereto being a center (see FIG. 1). That is, 16
straight lines that cross the cross-section are drawn so as to pass
through the midpoint of the long axis L and to form an equal
crossing angle at the midpoint (crossing angle: 11.25.degree.), to
thereby form 32 line segments from the midpoint to a surface of the
toner particle. Then, the line segments (division axes) from the
center to the surface layer of the toner particle are each defined
as An (n=1 to 32), the length of each of the line segments
(division axes) is defined as RAn, and the thickness of the surface
layer on the line segment An is defined as FRAn (n=1 to 32).
An average thickness Dav. of the surface layer containing the
organosilicon polymer in 32 portions on the line segments (division
axes) is determined through use of the above-mentioned parameters.
Further, a ratio of the number of the line segments out of the 32
line segments on each of which the thickness of the surface layer
containing the organosilicon polymer is 2.5 nm or less is
determined.
In the present invention, for averaging, an average value per toner
particle was calculated by measuring ten toner particles.
"Circle-Equivalent Diameter (Dtem) Determined Based on
Cross-Section of Toner Particle Obtained from Transmission Electron
Microscope (TEM) Image"
A circle-equivalent diameter (Dtem) determined based on a
cross-section of a toner particle obtained from a TEM image is
determined by the following method. First, regarding one toner
particle, a circle-equivalent diameter Dtem determined based on a
cross-section of the toner particle obtained from a TEM image is
determined by the following expression. [Circle-equivalent diameter
determined based on cross-section of toner particle obtained from
TEM image
(Dtem)]=(RA1+RA2+RA3+RA4+RA5+RA6+RA7+RA8+RA9+RA10+RA11+RA12+RA13+RA14+RA1-
5+RA16+RA17+RA18+RA19+RA20+RA21+RA22+RA23+RA24+RA25+RA26+RA27+RA28+RA29+RA-
30+RA31+RA32)/16
Circle-equivalent diameters of the ten toner particles are
determined, and an average value per toner particle is calculated
as a circle-equivalent diameter (Dtem) determined based on a
cross-section of a toner particle.
[Measurement of Average Thickness (Dav.) of Surface Layer of Toner
Particle]
An average thickness (Dav.) of a surface layer of a toner particle
is determined by the following method. First, an average thickness
D.sub.(n) of the surface layer of one toner particle is determined
by the following method. D.sub.(n)=(Total of thicknesses of surface
layer in 32 portions on division
axes)/32=(FRA1+FRA2+FRA3+FRA4+FRA5+FRA6+FRA7+FRA8+FRA9+FRA10+FRA11+FRA12+-
FRA13+FRA14+FRA15+FRA16+FRA17+FRA18+FRA19+FRA20+FRA21+FRA22+FRA23+FRA24+FR-
A25+FRA26+FRA27+FRA28+FRA29+FRA30+FRA31+FRA32)/32
In order to attain averaging, the average thickness (Dav.) of the
surface layer of the toner particle is obtained by determining the
average thickness D.sub.(n) (n=1 to 10) of the surface layer of the
toner particle as to ten toner particles, and calculating the
average value thereof per toner particle.
Dav.={D.sub.(1)+D.sub.(2)+D.sub.(3)+D.sub.(4)+D.sub.(5)+D.sub.(6)+D.sub.(-
7)+D.sub.(8)+D.sub.(9)+D.sub.(10)}/10
[Measurement of Ratio of Thickness of 2.5 nm or Less of Surface
Layer] [Ratio in which thickness (FRAn) of surface layer is 2.5 nm
or less]=[{Number of division axes in which thickness (FRAn) of
surface layer is 2.5 nm or less}/32].times.100
This calculation was performed on ten toner particles, and an
average value of the obtained ten ratios in which the thicknesses
(FRAn) of surface layers were 2.5 nm or less was determined as a
ratio in which the thickness (FRAn) of the surface layer of the
toner particle was 2.5 nm or less.
<Measurement Methods for Weight-Average Particle Diameter (D4)
and Number-Average Particle Diameter (D1) of Toner Particle>
The weight-average particle diameter (D4) and number-average
particle diameter (D1) of the toner particle are calculated as
described below. A precision particle size distribution measuring
apparatus based on a pore electrical resistance method provided
with a 100 .mu.m aperture tube "Coulter Counter Multisizer 3"
(trademark, manufactured by Beckman Coulter, Inc.) is used as a
measuring apparatus. Dedicated software included thereto "Beckman
Coulter Multisizer 3 Version 3.51" (manufactured by Beckman
Coulter, Inc.) is used for setting measurement conditions and
analyzing measurement data. The measurement is performed with the
number of effective measurement channels of 25,000.
An electrolyte aqueous solution prepared by dissolving reagent
grade sodium chloride in ion-exchanged water so as to have a
concentration of 1 mass %, for example, "ISOTON II" (manufactured
by Beckman Coulter, Inc.) can be used in the measurement.
The dedicated software was set as described below prior to the
measurement and the analysis.
In the "change standard measurement method (SOMME)" screen of the
dedicated software, the total count number of a control mode is set
to 50,000 particles, the number of times of measurement is set to
1, and a value obtained by using "standard particles having a
particle diameter of 10.0 .mu.m" (manufactured by Beckman Coulter,
Inc.) is set as a Kd value. A threshold and a noise level are
automatically set by pressing a "threshold/noise level measurement
button". In addition, a current is set to 1,600 .mu.A, a gain is
set to 2, and an electrolyte solution is set to ISOTON II, and a
check mark is placed in a check box as to whether the aperture tube
is flushed after the measurement.
In the "setting for conversion from pulse to particle diameter"
screen of the dedicated software, a bin interval is set to a
logarithmic particle diameter, the number of particle diameter bins
is set to 256, and a particle diameter range is set to the range of
from 2 .mu.m to 60 .mu.m.
A specific measurement method is as described below.
(1) About 200 ml of the electrolyte aqueous solution is charged
into a 250-milliliter round-bottom beaker made of glass dedicated
for Multisizer 3. The beaker is set in a sample stand, and the
electrolyte aqueous solution in the beaker is stirred with a
stirrer rod at 24 rotations/sec in a counterclockwise direction.
Then, dirt and bubbles in the aperture tube are removed by the
"aperture flush" function of the dedicated software.
(2) About 30 ml of the electrolyte aqueous solution is charged into
a 100-milliliter flat-bottom beaker made of glass. About 0.3 ml of
a diluted solution prepared by diluting "Contaminon N" (10 mass %
aqueous solution of a neutral detergent for washing a precision
measuring device formed of a nonionic surfactant, an anionic
surfactant, and an organic builder and having a pH of 7,
manufactured by Wako Pure Chemical Industries, Ltd.) with
ion-exchanged water by three parts by mass fold is added as a
dispersant to the electrolyte aqueous solution.
(3) An ultrasonic dispersing unit "Ultrasonic Dispension System
Tetra 150" (manufactured by Nikkaki Bios Co., Ltd.) in which two
oscillators each having an oscillatory frequency of 50 kHz are
built so as to be out of phase by 180.degree. and which has an
electrical output of 120 W is prepared. 3.3 L of ion-exchanged
water is charged into the water tank of the ultrasonic dispersing
unit. About 2 ml of the Contaminon N is charged into the water
tank.
(4) The beaker in the section (2) is set in the beaker fixing hole
of the ultrasonic dispersing unit, and the ultrasonic dispersing
unit is operated. Then, the height position of the beaker is
adjusted in order that the liquid level of the electrolyte aqueous
solution in the beaker may resonate with an ultrasonic wave from
the ultrasonic dispersing unit to the fullest extent possible.
(5) About 10 mg of the toner particles are gradually added to and
dispersed in the electrolyte aqueous solution in the beaker in the
section (4) under a state in which the electrolyte aqueous solution
is irradiated with the ultrasonic wave. Then, the ultrasonic
dispersion treatment is continued for an additional 60 seconds. The
temperature of water in the water tank is appropriately adjusted so
as to be 10.degree. C. or more and 40.degree. C. or less upon
ultrasonic dispersion.
(6) The electrolyte aqueous solution in the section (5) in which
the toner particles have been dispersed is dropped with a pipette
to the round-bottom beaker in the section (1) placed in the sample
stand, and the concentration of the toner particles to be measured
is adjusted to 5%. Then, measurement is performed until the
particle diameters of 50,000 particles are measured.
(7) The measurement data is analyzed with the dedicated software
included with the apparatus, and the weight-average particle
diameter (D4) and the number-average particle diameter (D1) are
calculated. An "average diameter" on the "analysis/volume
statistics (arithmetic average)" screen of the dedicated software
when the dedicated software is set to show a graph in a vol % unit
is the weight-average particle diameter (D4). In addition, an
"average diameter" on the "analysis/number statistics (arithmetic
average)" screen of the dedicated software when the dedicated
software is set to show a graph in a number % unit is the
number-average particle diameter (D1).
<Density of Silicon Atom (Atomic %) Existing in Surface of Toner
Particle>
The density of a silicon atom [dSi] (atomic %), the density of a
carbon atom [dC] (atomic %), and the density of an oxygen atom [dO]
(atomic %), the atoms existing in the surface of the toner
particle, are calculated by performing surface composition analysis
through use of X-ray photoelectron spectroscopic analysis (ESCA:
Electron Spectroscopy for Chemical Analysis).
In the present invention, an apparatus and measurement conditions
for ESCA are as described below. Used apparatus: Quantum 2000
manufactured by ULVAC-PHI, Inc. X-ray photoelectron spectrometer
measurement conditions: X-ray source: Al K.alpha. X-ray: 100 .mu.m,
25 W, 15 kV Raster: 300 .mu.m.times.200 .mu.m Pass energy: 58.70 eV
Step size: 0.125 eV Neutralization electron gun: 20 .mu.A, 1 V Ar
ion gun: 7 mA, 10 V Number of sweeps: Si: 15 sweeps, C: 10 sweeps,
O: 10 sweeps
In the present invention, the density of a silicon atom [dSi], the
density of a carbon atom [dC], and the density of an oxygen atom
[dO] (each represented in an atomic % unit), the atoms existing in
the surface of the toner particle, were calculated through use of a
relative sensitivity factor provided by PHI, Inc. based on the
measured peak intensity of each element.
Then, a ratio (atomic %) of the silicon atom density dSi to a total
(dC+dO+dSi) of the carbon atom density dC, the oxygen atom density
do, and the silicon atom density dSi of 100.0 atomic % in the
surface layer of the toner particle was determined.
<Glass Transition Temperatures (Tg)>
The glass transition temperatures (Tg) of the toner base particles
and the resin particles are measured with a differential scanning
calorimeter (DSC) M-DSC (trade name: Q2000, manufactured by TA
Instruments) by the following procedure. 3 mg of a sample to be
subjected to the measurement is precisely weighed. The sample is
loaded into an aluminum pan, and is subjected to the measurement
under normal temperature and normal humidity by using an empty
aluminum pan as a reference at a measurement temperature in the
range of from 20.degree. C. to 200.degree. C. and a rate of
temperature increase of 1.degree. C./min. At this time, the
measurement is performed at a modulation amplitude of
.+-.0.5.degree. C. and a frequency of 1/min. The glass transition
temperature (Tg: .degree. C.) is calculated from a reversing heat
flow curve to be obtained. A center value between the points of
intersection of baselines before and after heat absorption, and a
tangent to a curve based on the heat absorption is determined as
the Tg (.degree. C.).
<Acid Value>
The acid value is the number of milligrams of potassium hydroxide
required for neutralizing an acid contained in 1 g of a sample. The
acid value in the present invention is measured in accordance with
JIS K 0070-1992, specifically, the following procedure.
Titration is performed through use of a 0.1 mol/l potassium
hydroxide-ethyl alcohol solution (manufactured by Kishida Chemical
Co., Ltd.). A factor of the potassium hydroxide-ethyl alcohol
solution can be determined through use of a potentiometric titrator
(potentiometric titration measurement apparatus AT-510 manufactured
by Kyoto Electronics Manufacturing Co., Ltd.). 100 ml of 0.1 mol/l
hydrochloric acid is loaded into a 250-milliliter tall beaker and
titrated with the potassium hydroxide-ethyl alcohol solution, and
an acid value is determined based on the amount of the potassium
hydroxide-ethyl alcohol solution required for neutralization.
Hydrochloric acid prepared in accordance with JIS K 8001-1998 is
used as the 0.1 mol/l hydrochloric acid.
Measurement conditions in the acid value measurement are described
below. Titration: potentiometric titrator AT-510 (manufactured by
Kyoto Electronics Manufacturing Co., Ltd.) Electrode: combination
glass electrode, double junction type (manufactured by Kyoto
Electronics Manufacturing Co., Ltd.) Control software for titrator:
AT-WIN Software for analyzing titration: Tview Titration parameters
and control parameters in titration are as described below.
Titration Parameters Titr. mode: Blank Titration Titr. form: Full
Titration Max. Volume: 20 ml Wait Time before Titration: 30 s
Titration Direction: Auto Control Parameters End point judgment
potential: 30 dE End point judgment potential value: 50 dE/dmL End
point detection judgment: Not set Ctl. speed mode: Std Gain: 1 Data
samp. Pot.: 4 mV Data samp. Vol.: 0.1 ml
Main Test
0.100 g of a measurement sample is precisely weighed into a
250-milliliter tall beaker, and 150 ml of a mixed solution of
toluene and ethanol (3:1) is added to the beaker to dissolve the
sample over 1 hour. The solution is titrated with the potassium
hydroxide-ethyl alcohol solution through use of the above-mentioned
potentiometric titrator.
Blank Test
The same titration as that in the above-mentioned operation is
performed except that the sample is not used (that is, only the
mixed solution of toluene and ethanol (3:1) is used).
An acid value is calculated by substituting the result thus
obtained into the following expression.
A=[(C-B).times.f.times.5.611]/S (In the expression, A represents
the acid value (mgKOH/g), B represents the addition amount (ml) of
the potassium hydroxide-ethyl alcohol solution in the blank test, C
represents the addition amount (ml) of the potassium
hydroxide-ethyl alcohol solution in the main test, f represents the
factor of the potassium hydroxide solution, and S represents the
sample (g).)
<pKa>
0.100 g of a measurement sample is precisely weighed into a
250-milliliter tall beaker, and 150 ml of THF is added to the
beaker to dissolve the sample over 30 minutes. A pH electrode is
placed in this solution, and a pH of the THF solution of the sample
is read. After that, a 0.1 mol/l potassium hydroxide-ethyl alcohol
solution (manufactured by Kishida Chemical Co., Ltd.) is added by
10 .mu.l to the solution, and a pH is read and titration is
performed for every addition. The 0.1 mol/l potassium
hydroxide-ethyl alcohol solution is added until the pH reaches 10
or more and does not change even when 30 .mu.l of the potassium
hydroxide-ethyl alcohol solution is added. A pH is plotted against
the addition amount of the 0.1 mol/l potassium hydroxide-ethyl
alcohol solution based on the obtained result. Thus, a titration
curve is obtained. A point at which the tilt of a pH change becomes
maximum in the obtained titration curve is defined as a
neutralization point. A pKa is determined as described below. A pH
at a half of the amount of the 0.1 mol/l potassium hydroxide-ethyl
alcohol solution required up to the neutralization point is read
from the titration curve, and a value of the read pH is defined as
a pKa.
<NMR (Confirmation of Content of Monovalent Group a Contained in
Polymer A)>
A content of a monovalent group a contained in a polymer A is
measured through use of nuclear magnetic resonance spectrometric
analysis (.sup.1H-NMR) [400 MHz, CDCl.sub.3, room temperature
(25.degree. C.)]. Measurement apparatus: FT-NMR apparatus JNM-EX400
(manufactured by JEOL Ltd.) Measurement frequency: 400 MHz Pulse
condition: 5.0 .mu.s Frequency range: 10,500 Hz Number of scans: 64
scans
A molar ratio of each monomer component is determined based on a
value of integral of the obtained spectrum, and based on the molar
ratio, the mol % of the monovalent group a contained in the polymer
A is calculated.
<Median Diameter (D50) on Volume Basis of Resin
Particles>
A median diameter (D50) on a volume basis of resin particles is
calculated by measuring a particle diameter by dynamic light
scattering (DLS) through use of Zetasizer Nano-ZS (manufactured by
Malvern Instruments Ltd.).
First, a power source of an apparatus is turned on and kept in this
state for 30 minutes until a laser becomes stable. Then, Zetasizer
software is activated.
Manual is selected from a Measure menu, and the detail of the
measurement is input as described below. Measurement mode: particle
diameter Material: Polystyrene latex (RI: 1.59, Absorption: 0.01)
Dispersant: Water (Temperature: 25.degree. C., Viscosity: 0.8872
cP, RI: 1.330) Temperature: 25.0.degree. C. Cell: Clear disposable
zeta cell Measurement duration: Automatic
A sample is prepared by diluting with water so that the sample may
have a concentration of 0.50 mass %, and is filled into a
disposable capillary cell (DTS1060). The cell is loaded into a cell
holder of the apparatus.
When the above-mentioned preparation is finished, a Start button on
a measurement display screen is pressed to perform a
measurement.
The D50 is calculated based on data on a particle size distribution
on a volume basis, which is obtained by converting a light
intensity distribution obtained from a DLS measurement by the Mie
theory.
EXAMPLES
The present invention is described below in more detail by way of
specific production methods, Examples, and Comparative Examples.
However, the present invention is by no means limited thereto. The
number of parts and % in Examples and Comparative Examples are all
based on a mass unless otherwise specified.
Synthesis Example of Polymerizable Monomer M-1
18.0 g of 2,4-dihydroxybenzoic acid was dissolved in 150 mL of
methanol, and 36.9 g of potassium carbonate was added to the
solution. The resultant was heated to 65.degree. C. A mixed
solution of 18.7 g of 4-(chloromethyl)styrene and 100 mL of
methanol was dropped to the reaction liquid, and the resultant was
allowed to react at 65.degree. C. for 3 hours. The reaction liquid
was cooled and then filtered, and the filtrate was concentrated to
provide a crude product. The crude product was dispersed in 1.5 L
of water having a pH of 2 and extracted with ethyl acetate. Then,
the resultant was washed with water and dried with magnesium
sulfate. Ethyl acetate was distilled away under reduced pressure.
Thus, a precipitate was obtained. The precipitate was washed with
hexane, and was then refined by recrystallization with toluene and
ethyl acetate, to thereby provide 20.1 g of a polymerizable monomer
M-1 represented by the following formula (9).
##STR00005##
Synthesis Example of Polymerizable Monomer M-2
100 g of 2,5-dihydroxybenzoic acid and 1,441 g of 80% sulfuric acid
were mixed by heating to 50.degree. C. 144 g of tert-butyl alcohol
was added to the dispersion liquid, and the mixture was stirred at
50.degree. C. for 30 minutes. Then, the operation of adding 144 g
of tert-butyl alcohol to the dispersion liquid, followed by
stirring at 50.degree. C. for 30 minutes was repeated three times.
The reaction liquid was cooled to room temperature and slowly
poured into 1 kg of ice water. A precipitate was filtered and
washed with water, and was then washed with hexane. The resultant
precipitate was dissolved in 200 mL of methanol and re-precipitated
in 3.6 L of water. The resultant was filtrated and then dried at
80.degree. C. to provide 74.9 g of a salicylic acid intermediate
product represented by the following formula (10).
##STR00006##
20.1 g of a polymerizable monomer M-2 represented by the following
formula (11) was obtained in the same manner as in the
polymerizable monomer M-1 except that 25.0 g of the salicylic acid
intermediate product represented by the formula (10) was used
instead of 18.0 g of 2,4-dihydroxybenzoic acid.
##STR00007##
Synthesis Example of Polymerizable Monomer M-3
A salicylic acid intermediate product was obtained by the same
method as that of the synthesis of the polymerizable monomer M-2
except that 253 g of 2-octanol was used instead of 144 g of
tert-butyl alcohol. A polymerizable monomer M-3 represented by the
following formula (12) was obtained by the same method as that of
the synthesis example of the polymerizable monomer M-1 except that
32 g of the salicylic acid intermediate product obtained here was
used.
##STR00008##
Synthesis Example of Polymerizable Monomer M-4
A polymerizable monomer M-4 represented by the following formula
(13) was obtained by the same method as that of the synthesis
example of the polymerizable monomer M-1 except that 18 g of
2,3-dihydroxybenzoic acid was used instead of 18.0 g of
2,4-dihydroxybenzoic acid.
##STR00009##
Synthesis Example of Polymerizable Monomer M-5
A polymerizable monomer M-5 represented by the following formula
(14) was obtained by the same method as that of the synthesis
example of the polymerizable monomer M-1 except that 18 g of
2,6-dihydroxybenzoic acid was used instead of 18.0 g of
2,4-dihydroxybenzoic acid.
##STR00010##
Synthesis Example of Polymerizable Monomer M-6
A polymerizable monomer M-6 represented by the following formula
(15) was obtained by the same method as that of the synthesis
example of the polymerizable monomer M-1 except that 18 g of
2,5-dihydroxy-3-methoxybenzoic acid was used instead of 18.0 g of
2,4-dihydroxybenzoic acid. In the formula (15), Me represents a
methyl group.
##STR00011##
Synthesis Example of Polymer A-1
8.6 g of the polymerizable monomer M-1 represented by the formula
(9) and 61.4 g of styrene were dissolved in 42.0 ml of
N,N-Dimethylformamide (DMF), and the mixture was stirred for 1 hour
with nitrogen bubbling and then heated to 110.degree. C. A mixed
solution of 2.1 g of tert-butylperoxy isopropyl monocarbonate
(trade name: Perbutyl I, manufactured by NOF Corporation (previous
corporate name: Nippon Oil and Fats Co., Ltd.)) and 42 ml of
toluene, the mixed solution serving as an initiator, was dropped to
the reaction liquid. Further, the resultant was allowed to react at
110.degree. C. for 4 hours. Then, the resultant was cooled and
dropped to 1 L of methanol, to thereby provide a precipitate. The
obtained precipitate was dissolved in 120 ml of THF and then
dropped to 1.80 L of methanol to precipitate a white precipitate.
The resultant was filtered and dried at 90.degree. C. under reduced
pressure to provide 66.5 g of a polymer A-1. An NMR and an acid
value of the obtained polymer A-1 were measured to confirm a
content of a component derived from the polymerizable monomer
M-1.
Polymer A-2 to Polymer A-9
A polymer A-2 to a polymer A-9 were obtained in the same manner as
in the synthesis example of the polymer A-1 except that loading
amounts of raw materials were changed as shown in Table 1.
Synthesis Example of Polymer B-1
200 parts by mass of xylene was loaded into a reaction vessel
provided with a stirrer, a condenser, a thermometer, and a nitrogen
introducing tube, and refluxed in a stream of nitrogen.
Next, the following substances were mixed, dropped to the reaction
vessel with stirring, and the mixture was maintained for 10
hours.
TABLE-US-00001 1-Vinylnaphthalene-2-carboxylic acid 5.3 parts by
mass Styrene 75.0 parts by mass 2-Ethylhexyl acrylate 16.0 parts by
mass Dimethyl 2,2'-azobis(2-methylpropionate) 5.0 parts by mass
After that, a solvent was distilled away by distillation, and the
residue was dried at 40.degree. C. under reduced pressure to
provide a polymer B-1. An NMR and an acid value of the obtained
polymer B-1 were measured to confirm a content of the monovalent
group a represented by the formula (2).
Synthesis Example of Polymer B-2
A polymer B-2 was obtained in the same manner as in the polymer B-1
except that 9.0 parts by mass of 5-vinylsalicylic acid was used
instead of 5.3 parts by mass of 1-vinylnaphthalene-2-carboxylic
acid in the synthesis example of the polymer B-1.
Synthesis Example of Polymer B-3
200.0 parts of xylene was loaded into a reaction vessel provided
with a stirrer, a condenser, a thermometer, and a nitrogen
introducing tube, and was refluxed in a stream of nitrogen. 6.0
parts by mass of 2-acrylamido-2-methylpropanesulfonic acid, 72.0
parts by mass of styrene, and 18.0 parts by mass of 2-ethylhexyl
acrylate were mixed as monomers, and the mixture was dropped to the
reaction vessel with stirring, and the liquid was maintained for 10
hours. After that, the solvent was distilled away by distillation,
and the residue was dried under reduced pressure at 40.degree. C.
to provide a polymer B-3. An NMR and an acid value of the obtained
polymer B-3 were measured to confirm a content of the monovalent
group a represented by the formula (2).
Physical properties of the obtained polymer A-1 to polymer A-9 and
polymer B-1 to polymer B-3 are shown in Table 1.
TABLE-US-00002 TABLE 1 Content of monovalent Weight- group a
Polymerizable monomer M average represented Acid Loading molecular
by dissociation amount weight Tg formula (2) constant Kind (g) St
2EHA BA HEMA Initiator (Mw) (.degree. C.) (.mu.mol/g) pKa Polymer
A-1 Polymerizable 8.6 61.4 0.0 0.0 0.0 2.1 28,200 108.9 452 7.3
monomer M-1 Polymer A-2 Polymerizable 8.0 51.5 0.0 10.5 0.0 2.1
30,300 83.2 421 7.0 monomer M-1 Polymer A-3 Polymerizable 10.8 59.2
0.0 0.0 0.0 2.1 28,200 106.2 473 7.2 monomer M-2 Polymer A-4
Polymerizable 11.7 58.3 0.0 0.0 0.0 2.1 30,000 107.2 438 7.3
monomer M-3 Polymer A-5 Polymerizable 8.2 58.6 0.0 0.0 3.2 2.1
31,100 106.7 432 7.5 monomer M-1 Polymer A-6 Polymerizable 8.4 61.6
0.0 0.0 0.0 2.1 29,500 105.3 445 7.6 monomer M-4 Polymer A-7
Polymerizable 8.7 61.3 0.0 0.0 0.0 2.1 30,100 110.2 461 7.8 monomer
M-5 Polymer A-8 Polymerizable 8.3 46.3 15.4 0.0 0.0 2.1 29,500 70.5
397 8.0 monomer M-6 Polymer A-9 Polymerizable 8.0 46.5 0.0 0.0 15.5
2.1 16,800 86.3 425 8.5 monomer M-1 Polymer B-1 Described in
specification 15,600 91.4 0 8.8 Polymer B-2 Described in
specification 14,400 75.2 0 6.6 Polymer B-3 Described in
specification 24,500 68.9 0 -0.6 St: styrene 2EHA: 2-ethylhexyl
acrylate BA: butyl acrylate HEMA: 2-hydroxyethyl methacrylate
Production Example of Aqueous Dispersion of Resin Particles E-1
200.0 parts by mass of methyl ethyl ketone was loaded into a
reaction vessel provided with a stirrer, a condenser, a
thermometer, and a nitrogen introducing tube, and 100.0 parts by
mass of the polymer A-1 was added to the mixture to be dissolved
therein. Then, a 1.0 N potassium hydroxide aqueous solution was
slowly added to the resultant and the mixture was stirred for 10
minutes. Then, 500.0 parts by mass of ion-exchanged water was
slowly dropped to emulsify the resultant.
The solvent was removed by subjecting the obtained emulsion to
distillation under reduced pressure, and ion-exchanged water was
added to the resultant so that the concentration of the resin was
adjusted to 20%. Thus, an aqueous dispersion of resin particles E-1
was obtained. Physical property values of the obtained aqueous
dispersion of the resin particles E-1 are shown in Table 2.
Production Examples of Aqueous Dispersions of Resin Particles E-2
to Resin Particles E-19
Aqueous dispersions of resin particles E-2 to resin particles E-14
were obtained in the same manner as in the production example of
the resin particles E-1 except that the amounts the polymer A-1 and
the 1.0 N potassium hydroxide aqueous solution were changed as
shown in Table 2. Physical property values of the obtained aqueous
dispersions of the resin particles E-2 to the resin particles E-14
are shown in Table 2.
TABLE-US-00003 TABLE 2 Amount of KOH Particle diameter Aqueous
dispersion Kind of polymer (parts by mass) D50 (nm) Resin particles
E-1 Polymer A-1 40.1 40 Resin particles E-2 Polymer A-2 37.3 52
Resin particles E-3 Polymer A-3 41.8 42 Resin particles E-4 Polymer
A-4 38.8 46 Resin particles E-5 Polymer A-5 36.0 64 Resin particles
E-6 Polymer A-6 37.0 51 Resin particles E-7 Polymer A-7 38.4 49
Resin particles E-8 Polymer A-8 31.0 82 Resin particles E-9 Polymer
A-9 37.6 73 Resin particles E-10 Polymer B-1 35.0 100 Resin
particles E-11 Polymer B-2 49.9 72 Resin particles E-12 Polymer A-1
23.6 198 Resin particles E-13 Polymer B-3 35.4 56
Production Example of Polyester-Based Resin
(Synthesis of Isocyanate Group-Containing Prepolymer)
TABLE-US-00004 Bisphenol A-ethylene oxide (2 mol) adduct 725 parts
by mass Phthalic acid 290 parts by mass Dibutyltin oxide 3.0 parts
by mass
The above-mentioned materials were allowed to react with stirring
at 220.degree. C. for 7 hours and further allowed to react under
reduced pressure for 5 hours. Then, the resultant was cooled to
80.degree. C. and allowed to react with 190 parts by mass of
isophorone diisocyanate in ethyl acetate for 2 hours. Thus, an
isocyanate group-containing polyester resin was obtained. 25 parts
by mass of the isocyanate group-containing polyester resin and 1
part by mass of isophorone diamine were allowed to react at
50.degree. C. for 2 hours, to thereby provide a polyester-based
resin containing, as a main component, polyester containing a urea
group. The obtained polyester-based resin had a weight-average
molecular weight (Mw) of 22,300, a number-average molecular weight
(Mn) of 2,980, and a peak molecular weight of 7,200.
Example 1
700 parts by mass of ion-exchanged water, 1,000 parts by mass of a
0.1 mol/L Na.sub.3PO.sub.4 aqueous solution, and 24.0 parts by mass
of a 1.0 mol/L HCl aqueous solution were added to a five-necked
pressure-resistant vessel provided with a reflux tube, a stirrer, a
thermometer, and a nitrogen introducing tube. The mixture was kept
at 63.degree. C. with stirring at 12,000 rpm through use of a
high-speed stirring device TK-homomixer. 85 parts by mass of a 1.0
mol/L CaCl.sub.2 aqueous solution was gradually added to the
resultant. Thus, an aqueous dispersion medium containing a fine
poorly water-soluble dispersion stabilizer Ca.sub.3(PO.sub.4).sub.2
was prepared.
After that, a polymerizable monomer composition was produced by
using the following raw materials. This step is defined as a
dissolving step.
TABLE-US-00005 Styrene monomer 75.0 parts by mass n-Butyl acrylate
25.0 parts by mass Divinylbenzene 0.1 part by mass Organosilicon
compound (methyltriethoxysilane) 15.0 parts by mass Copper
phthalocyanine pigment (Pigment Blue 6.5 parts by mass 15:3)
Polyester-based resin 6.0 parts by mass Release agent (behenyl
behenate) 10.0 parts by mass
The above-mentioned raw materials were dispersed with an attritor
(manufactured by Nippon Coke & Engineering Co., Ltd.) for 3
hours to provide a polymerizable monomer composition. Then, the
polymerizable monomer composition was transferred into another
vessel and kept at 63.degree. C. for 5 minutes with stirring. Then,
20.0 parts by mass of t-butyl peroxypivalate (50% toluene solution)
serving as a polymerization initiator were added to the
polymerizable monomer composition, and the resultant was kept for 5
minutes with stirring (dissolving step).
Then, the polymerizable monomer composition was loaded into the
aqueous dispersion medium and granulated for 10 minutes with
stirring with a high-speed stirring device (granulating step).
After that, the high-speed stirring device was replaced by a
propeller type stirrer, and the internal temperature was raised to
70.degree. C. It took minutes to raise the temperature. Further,
the resultant was allowed to react for 5 hours with slow stirring.
The pH was 5.1. The step up to here is defined as a reaction 1
step.
Next, the pH was adjusted to 8.0 within 10 minutes by adding a 1.0
N NaOH aqueous solution to the resultant, and the temperature
inside the vessel was raised to 85.degree. C. It took 20 minutes to
raise the temperature. Then, the inside of the vessel was kept at
85.degree. C. for 3.0 hours. The step up to here is defined as a
reaction 2 step.
After the completion of the reaction 2 step, the reflux tube was
removed, and a distillation device capable of recovering a fraction
was mounted on the vessel. Then, the temperature inside the vessel
was raised to 100.degree. C. It took 30 minutes to raise the
temperature. After that, the temperature inside the vessel was kept
at 100.degree. C. for 5.0 hours. The step from the mounting of the
distillation device capable of recovering a fraction on the vessel
to the completion of the keeping of the vessel at 100.degree. C.
for 5.0 hours is defined as a distillation step. Further, the
temperature to be kept was defined as a distillation temperature,
and the time during which the temperature was kept was defined as a
distillation time. In this step, a residual monomer and other
solvents were removed. A small amount of matters in the vessel at
the beginning of the distillation and at the end thereof were taken
out, and the pH thereof at 85.degree. C. was measured to be 8.0 in
both cases.
After the completion of the distillation, the vessel was cooled to
90.degree. C., and 3.2 parts by mass (solid content: 0.64 part by
mass) of an aqueous dispersion of the resin particles E-1 was
dropped to the vessel over 10 minutes. After that, the inside of
the vessel was kept at 90.degree. C. for 1.0 hour. The step up to
here is defined as a resin particle sticking step.
After the resin particle sticking step, the vessel was cooled to
30.degree. C., and diluted hydrochloric acid was added to the
vessel to decrease the pH to 1.5. Then, a dispersion stabilizer was
dissolved in the resultant, further followed by filtration. After
the filtration, 700 parts by mass of ion-exchanged water was
further added to the resultant without taking out an obtained cake,
and the mixture was subjected again to filtration and washing.
Next, the cake after the filtration was taken out and dried in a
vacuum at 30.degree. C. for 1 hour. Particles obtained here are
defined as toner particles.
Further, fine and coarse powders were cut by pneumatic
classification. Particles thus obtained are defined as a toner. The
formulation and production conditions of the toner particles and
the toner are shown in Table 3, and the physical properties of
toner particles are shown in Table 4. In Table 4, "ESCA dSi value"
represents ratio of silicon atom density dSi with respect to total
of 100.0 atomic % of carbon atom density dC, oxygen atom density
dO, and silicon atom density dSi on the surface of the toner
particle in X-ray photoelectron spectroscopic analysis of surface
of toner particle.
A toner 1 thus obtained was evaluated as described below.
A tandem-type laser beam printer LBP9510C manufactured by Canon
Inc. having a configuration as illustrated in FIG. 3 was remodeled
so as to be capable of performing printing only with a cyan
station. The tandem-type laser beam printer LBP9510C was also
remodeled so that a transfer current was able to be set
arbitrarily. In FIG. 3, there are illustrated a photosensitive
member (elestrostatic charge image-bearing member) 1, a toner
bearing member 2, a supplying roller 3, a toner 4, a regulating
blade 5, a toner container 6, exposure light 7, a charging roller
8, a cleaning device 9, a transfer roller 13, an intermediate
transfer belt 16, a transfer member (recording paper) 18, and a
fixing device 21. A toner cartridge for the LBP9510C was used, and
200 g of the toner was filled into the toner cartridge. Then, the
toner cartridge was left to stand for 3 days under a
high-temperature and high-humidity (H/H) (32.5.degree. C./85% RH)
environment. After being left to stand for 3 days under the
high-temperature and high-humidity (H/H) environment, the toner
cartridge was mounted on the LBP9510C, and a transfer latitude, an
image density, and chargeability in an initial stage were
evaluated. After that, an image having a printing ratio of 1.0% was
printed out onto 15,000 sheets of A4 paper in a lateral direction,
and a transfer latitude, an image density, and chargeability, after
the output of the 15,000 sheets of paper (after endurance) were
evaluated. The results are shown in Table 5.
<Transfer Latitude>
The transfer current was changed in 2 .mu.A steps from 2 .mu.A to
20 .mu.A in the initial stage and after the printing of the 15,000
sheets of paper. A solid image was output in each step, and a
transfer residual toner on the photosensitive member after the
transfer of the solid image was scraped off by taping of a Mylar
tape. Then, the tape and a tape that was not used for taping were
attached onto a letter-size XEROX 4200 sheet (manufactured by Xerox
Corporation, 75 g/m.sup.2). Transferability was evaluated based on
a numerical value obtained by subtracting a reflectance Dr (%) of
the tape attached to the sheet without being used for taping from a
reflectance Ds (%) of the tape.
A transfer current range in which the numerical value of
transferability was 2.0 or less was defined as a transfer latitude.
As the transfer current range widens, the result of the transfer
latitude becomes more satisfactory.
The reflectance was measured by using "REFLECTOMETER MODEL TC-6DS"
(manufactured by Tokyo Denshoku Co., Ltd.) with an amber filter
mounted thereto.
<Image Density>
In the initial stage and after the output of the 15,000 sheets of
paper, a sample image, which had 20-millimeter square solid black
images printed at four corners and a center of a sheet surface, was
output, and an average density at those five points was measured.
The image density was obtained by measuring a density relative to
an image in a white ground portion having an original density of
0.00 through use of "Macbeth reflection densitometer RD918"
(manufactured by Macbeth).
<Chargeability>
In the initial stage and after the output of the 15,000 sheets of
paper, the toner was removed from the cartridge, and a
two-component developer was produced in each step as described
below.
In order to evaluate a charge quantity, a sample was prepared as
described below. 18.6 g of a magnetic carrier F813-300
(manufactured by Powdertech Co., Ltd.) and 1.4 g of an evaluation
toner were loaded into a 50 cc plastic bottle with a cover, and
shaken with a shaker (YS-LD: manufactured by Yayoi Co., Ltd.) for 1
minute at a speed of 2 rounds per second.
Regarding the toner and the two-component developer, evaluations
were carried out as described below.
<Evaluation of Toner Charge Quantity Under High Temperature and
High Humidity>
A charge quantity was obtained by leaving a two-component developer
to stand under a high-temperature and high-humidity environment
(32.5.degree. C./85% RH) for 3 days, shaking the two-component
developer for 3 minutes at a speed of 200 times/minute, and
measuring a toner charge quantity through use of an apparatus of
FIG. 4.
(Measurement Method for Charge Quantity)
0.500 g of a two-component developer to be measured for
triboelectric charge quantity is loaded into a metallic measurement
vessel 42 having a 500-mesh (mesh size: 25 .mu.m) screen 43
arranged on a bottom illustrated in FIG. 4, and the measurement
vessel 42 is covered with a metallic cover 44. At this time, the
entire measurement vessel 42 is weighed, and the obtained weight is
defined as W1 (g). Then, in a suction machine 41 (at least a
portion that is held in contact with the measurement vessel 42 is
made of an insulator), an air volume regulation valve 46 is
adjusted by performing suction through a suction port 47, to
thereby set the pressure of a vacuum gauge 45 to 250 mmAq. In this
state, suction is performed sufficiently, preferably for 2 minutes,
to remove a toner from the two-component developer by suction.
The potential of an electrometer 49 in this case is defined as V
(volt). There is provided a condenser 48, and the capacity thereof
is defined as C (.mu.F). The entire measurement vessel after the
suction is weighed, and the obtained weight is defined as W2 (g).
The triboelectric charge quantity of the toner is calculated by the
following expression. Triboelectric charge quantity
(mC/kg)=(C.times.V)/(W1-W2)
As the obtained charge quantity is larger, and the difference
between the charge quantity in the initial stage and the charge
quantity after the printing of the 15,000 sheets of paper is
smaller, it is understood that better results are obtained.
Example 2 to Example 30, and Example 33 and Example 34
Toner particles and toners were produced in accordance with the
production conditions and formulations shown in Table 3, and in
accordance with the other conditions in Example 1. The physical
properties of the obtained toner particles are shown in Table 4.
Further, the evaluation results are shown in Table 5. Methods for
distillation under reduced pressure and distillation under pressure
are described below.
The distillation under reduced pressure was performed by mounting a
pressure reducer on an open port and reducing pressure to such a
degree that a toner was not sucked toward a side closer to the
distillation device configured to recover a fraction.
The distillation under pressure was performed by mounting a
pressurizer on an open port and mounting a valve on the side closer
to the distillation device so that a toner was not influenced by
pressure. During distillation, the valve on the side closer to the
distillation device was opened once every 5 minutes to return the
pressure to normal pressure, and volatile portions were
recovered.
Example 31
Toner particles were obtained in accordance with Example 1 except
that the resin particle sticking step was not performed.
The aqueous dispersion of the resin particles E-1 was dried to
provide a dried product of the resin particles E-1. The obtained
dried product of the resin particles E-1 was frozen and pulverized
to provide a frozen and pulverized product of the resin particles
E-1.
0.5 part by mass of the frozen and pulverized product of the resin
particles E-1 was added to 100.0 parts by mass of the dried toner
particles, and the mixture was loaded into a dry particle
compounding device (Nobilta NOB-130 manufactured by Hosokawa Micron
Corporation). The resin particles E-1 were stuck to the toner
particles under the conditions of a treatment temperature of
30.degree. C. and a speed of a rotary treatment blade of 90 m/sec.
to provide toner particles 31. Further, fine and coarse powders
were cut by pneumatic classification. Particles thus obtained are
defined as a toner 31. The physical properties of the toner
particles 31 are shown in Table 4. The toner 31 was evaluated in
the same manner as in Example 1, and the results are shown in Table
5.
Example 32
The process up to the reaction 1 step was performed in accordance
with Example 1.
After the completion of the reaction 1 step, the pH was adjusted to
8.0 within 10 minutes by adding a 1.0 N NaOH aqueous solution to
the resultant, and 3.2 parts by mass (solid content: 0.6 part by
mass) of the aqueous dispersion of the resin particles E-1 was
dropped to the vessel over 10 minutes. After that, the inside of
the vessel was raised to 85.degree. C. It took 20 minutes to raise
the temperature. Then, the inside of the vessel was kept at
85.degree. C. for 3.0 hours.
Next, the reflux tube was removed, and a distillation device
capable of recovering a fraction was mounted on the vessel. Then,
the temperature inside the vessel was raised to 100.degree. C. It
took 30 minutes to raise the temperature. After that, the
temperature inside the vessel was kept at 100.degree. C. for 5.0
hours. The step from the mounting of the distillation device
capable of recovering a fraction on the vessel to the completion of
the keeping of the vessel at 100.degree. C. for 5.0 hours is
defined as a distillation step. Further, the temperature to be kept
was defined as a distillation temperature, and the time during
which the temperature was kept was defined as a distillation time.
In this step, a residual monomer and other solvents were removed. A
small amount of matters in the vessel at the beginning of the
distillation and at the end thereof were taken out, and the pH
thereof at 85.degree. C. was measured to be 8.0 in both cases. The
vessel was cooled to 30.degree. C., and diluted hydrochloric acid
was added to the vessel to decrease the pH to 1.5. Then, a
dispersion stabilizer was dissolved in the resultant, further
followed by filtration. After the filtration, 700 parts by mass of
ion-exchanged water was further added to the resultant without
taking out an obtained cake, and the mixture was subjected again to
filtration and washing.
Next, the cake after the filtration was taken out and dried in a
vacuum at 30.degree. C. for 1 hour. Particles obtained here are
defined as toner particles.
Further, fine and coarse powders were cut by pneumatic
classification. Particles thus obtained are defined as a toner 32.
The physical properties of toner particles 32 are shown in Table 4.
The toner 32 was evaluated in the same manner as in Example 1, and
the results are shown in Table 5.
Comparative Example 1 to Comparative Example 3
Toner particles and toners were produced in accordance with the
production conditions and formulations shown in Table 3, and in
accordance with the other conditions in Example 1. The physical
properties of the obtained toner particles are shown in Table 4.
Further, the resultant toners were evaluated in the same manner as
in Example 1, and the results are shown in Table 5. Methods for
distillation under reduced pressure and distillation under pressure
are described below.
The distillation under reduced pressure was performed by mounting a
pressure reducer on an open port and reducing pressure to such a
degree that a toner was not sucked toward a side closer to the
distillation device configured to recover a fraction.
The distillation under pressure was performed by mounting a
pressurizer on an open port and mounting a valve on the side closer
to the distillation device so that a toner was not influenced by
pressure. During distillation, the valve on the side closer to the
distillation device was opened once every 5 minutes to return the
pressure to normal pressure, and volatile portions were
recovered.
Comparative Example 4
The process up to the distillation step was performed in accordance
with Example 1 except that the raw materials to be used in the
polymerizable monomer composition of Example 1 were changed to the
following materials.
TABLE-US-00006 Styrene monomer 75.0 parts by mass n-Butyl acrylate
25.0 parts by mass Divinylbenzene 0.1 part by mass Polymer A-1 0.5
part by mass Copper phthalocyanine pigment 6.5 parts by mass
(Pigment Blue 15:3) Polyester-based resin 6.0 parts by mass Release
agent [behenyl behenate] 10.0 parts by mass
After the completion of the distillation step, the vessel was
cooled to 30.degree. C., and diluted hydrochloric acid was added to
the vessel to decrease the pH to 1.5. Then, a dispersion stabilizer
was dissolved in the resultant, further followed by filtration.
After the filtration, 700 parts by mass of ion-exchanged water was
further added to the resultant without taking out an obtained cake,
and the mixture was subjected again to filtration and washing.
Next, the cake after the filtration was taken out and dried in a
vacuum at 30.degree. C. for 1 hour. Particles obtained here are
defined as toner particles 38.
Further, fine and coarse powders were cut by pneumatic
classification. After that, 2.0 parts by mass of hydrophobic silica
fine powder was mixed with 100.0 parts by mass of the toner
particles 38 by using a Henschel mixer (manufactured by Mitsui
Miike Machinery Co., Ltd.) at 3,000 rpm for 15 minutes. Thus, a
toner 38 was obtained. Powder treated with dimethylsilicone oil (20
mass %) serving as a flow improver, the powder having a
number-average primary particle diameter of 10 nm and a BET
specific surface area of 170 m.sup.2/g, was used as the hydrophobic
silica fine powder. The particles thus obtained were defined as a
toner 38. The physical properties of the toner particles 38 are
shown in Table 4. The obtained toner 38 was evaluated in the same
manner as in Example 1, and the results are shown in Table 5.
TABLE-US-00007 TABLE 3 Addition Tem- amount per- of ature organo-
of Time Distil- silicon reac- of pH lation Distil- com- tion
reaction of temper- lation Organosilicon pound 2 2 reaction ature
Distillation time compound (parts) (.degree. C.) (hr) 2 (.degree.
C.) method (hr) Example 1 Toner 1 Methyltriethoxysilane 15.0 85 3
8.0 100 Distillation under 5 normal pressure Example 2 Toner 2
Ethyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5 normal
pressure Example 3 Toner 3 Butyltriethoxysilane 15.0 85 3 8.0 100
Distillation under 5 normal pressure Example 4 Toner 4
Hexyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5 normal
pressure Example 5 Toner 5 Phenyltriethoxysilane 15.0 85 3 8.0 100
Distillation under 5 normal pressure Example 6 Toner 6
Ethyltriethoxysilane 15.0 75 5 8.0 75 Distillation under 8 normal
pressure Example 7 Toner 7 Ethyltriethoxysilane 15.0 80 3 8.0 80
Distillation under 5 normal pressure Example 8 Toner 8
Ethyltriethoxysilane 15.0 85 3 8.0 80 Distillation under 5 reduced
pressure Example 9 Toner 9 Ethyltriethoxysilane 15.0 90 3 8.0 90
Distillation under 5 reduced pressure Example 10 Toner 10
Ethyltriethoxysilane 15.0 90 3 8.0 95 Distillation under 5 normal
pressure Example 11 Toner 11 Methyltriethoxysilane 15.0 85 3 8.0
100 Distillation under 5 normal pressure Example 12 Toner 12
Methyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5 normal
pressure Example 13 Toner 13 Methyltriethoxysilane 15.0 85 3 8.0
100 Distillation under 5 normal pressure Example 14 Toner 14
Methyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5 normal
pressure Example 15 Toner 15 Methyltriethoxysilane 15.0 85 3 8.0
100 Distillation under 5 normal pressure Example 16 Toner 16
Methyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5 normal
pressure Example 17 Toner 17 Methyltriethoxysilane 15.0 85 3 8.0
100 Distillation under 5 normal pressure Example 18 Toner 18
Methyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5 normal
pressure Example 19 Toner 19 Methyltriethoxysilane 15.0 85 3 8.0
100 Distillation under 5 normal pressure Example 20 Toner 20
Methyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5 normal
pressure Example 21 Toner 21 Methyltriethoxysilane 15.0 85 3 8.0
100 Distillation under 5 normal pressure Example 22 Toner 22
Methyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5 normal
pressure Example 23 Toner 23 Methyltriethoxysilane 15.0 85 3 8.0
100 Distillation under 5 normal pressure Example 24 Toner 24
Methyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5 normal
pressure Example 25 Toner 25 Methyltriethoxysilane 15.0 85 3 8.0
100 Distillation under 5 normal pressure Example 26 Toner 26
Methyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5 normal
pressure Example 27 Toner 27 Methyltriethoxysilane 38.0 85 3 8.0
108 Distillation under 8 pressure Example 28 Toner 28
Methyltriethoxysilane 25.0 85 3 8.0 105 Distillation under 8
pressure Example 29 Toner 29 Methyltriethoxysilane 7.0 85 3 8.0 100
Distillation under 5 normal pressure Example 30 Toner 30
Methyltriethoxysilane 6.0 85 3 8.0 100 Distillation under 5 normal
pressure Example 31 Toner 31 Methyltriethoxysilane Described in
specification Example 32 Toner 32 Methyltriethoxysilane Described
in specification Example 33 Toner 33 Methyltriethoxysilane 15.0 85
3 8.0 100 Distillation under 5 normal pressure Example 34 Toner 34
Methyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5 normal
pressure Comparative Toner 35 Hexyltriethoxysilane 5.0 70 3 8.0 70
Distillation under 5 Example 1 reduced pressure Comparative Toner
36 Hexyltriethoxysilane 6.5 70 3 7.0 70 Distillation under 5
Example 2 reduced pressure Comparative Toner 37
Methyltriethoxysilane 15.0 85 3 8.0 100 Distillation under 5
Example 3 normal pressure Comparative Toner 38 None Described in
specification Example 4 Addition Number Stick- number of parts
Addi- ing of parts of solid tion time of aqueous content pH
Addition of Addition dispersion of of temperature resin timing
Resin of resin resin resin of resin parti- pH of of resin parti-
particles particles parti- particles cles distillation particles
cles (parts) (parts) cles (.degree. C.) (hr) Example 1 Toner 1 8.0
After E-1 3.2 0.6 8.0 90 1.0 distillation Example 2 Toner 2 8.0
After E-1 3.2 0.6 8.0 90 1.0 distillation Example 3 Toner 3 8.0
After E-1 3.2 0.6 8.0 90 1.0 distillation Example 4 Toner 4 8.0
After E-1 3.2 0.6 8.0 90 1.0 distillation Example 5 Toner 5 8.0
After E-1 3.2 0.6 8.0 90 1.0 distillation Example 6 Toner 6 8.0
After E-1 3.2 0.6 8.0 90 1.0 distillation Example 7 Toner 7 8.0
After E-1 3.2 0.6 8.0 90 1.0 distillation Example 8 Toner 8 8.0
After E-1 3.2 0.6 8.0 90 1.0 distillation Example 9 Toner 9 8.0
After E-1 3.2 0.6 8.0 90 1.0 distillation Example 10 Toner 10 8.0
After E-1 3.2 0.6 8.0 90 1.0 distillation Example 11 Toner 11 8.0
After E-1 0.6 0.1 8.0 90 1.0 distillation Example 12 Toner 12 8.0
After E-1 1.6 0.3 8.0 90 1.0 distillation Example 13 Toner 13 8.0
After E-1 2.6 0.5 8.0 90 1.0 distillation Example 14 Toner 14 8.0
After E-1 6.4 1.3 8.0 90 1.0 distillation Example 15 Toner 15 8.0
After E-1 15.4 3.1 8.0 90 1.0 distillation Example 16 Toner 16 8.0
After E-1 16.7 3.3 8.0 90 1.0 distillation Example 17 Toner 17 8.0
After E-2 3.2 0.6 8.0 85 1.0 distillation Example 18 Toner 18 8.0
After E-3 3.2 0.6 8.0 90 1.0 distillation Example 19 Toner 19 8.0
After E-4 3.2 0.6 8.0 90 1.0 distillation Example 20 Toner 20 8.0
After E-5 3.2 0.6 8.0 90 1.0 distillation Example 21 Toner 21 8.0
After E-6 3.2 0.6 8.0 90 1.0 distillation Example 22 Toner 22 8.0
After E-7 3.2 0.6 8.0 90 1.0 distillation Example 23 Toner 23 8.0
After E-8 3.2 0.6 8.0 70 1.0 distillation Example 24 Toner 24 8.0
After E-9 3.2 0.6 8.0 90 1.0 distillation Example 25 Toner 25 8.0
After E-10 3.2 0.6 8.0 90 1.0 distillation Example 26 Toner 26 8.0
After E-11 3.2 0.6 8.0 75 1.0 distillation Example 27 Toner 27 8.0
After E-1 3.4 0.7 8.0 90 1.0 distillation Example 28 Toner 28 8.0
After E-1 3.3 0.7 8.0 90 1.0 distillation Example 29 Toner 29 8.0
After E-1 1.6 0.3 8.0 90 1.0 distillation Example 30 Toner 30 8.0
After E-1 1.6 0.3 8.0 90 1.0 distillation Example 31 Toner 31
Described in specification Example 32 Toner 32 Described in
specification Example 33 Toner 33 8.0 After E-12 31.9 6.4 8.0 90
1.0 distillation Example 34 Toner 34 8.0 After E-1 19.2 3.8 8.0 70
1.0 distillation Comparative Toner 35 8.0 After E-1 1.5 0.3 8.0 90
1.0 Example 1 distillation Comparative Toner 36 7.0 After E-1 1.5
0.3 8.0 90 1.0 Example 2 distillation Comparative Toner 37 8.0
After E-13 3.2 0.6 8.0 70 1.0 Example 3 distillation Comparative
Toner 38 Described in specification Example 4
TABLE-US-00008 TABLE 4 Organosilicon polymer in toner particle
Weight- Ratio of peak Ratio of average area for Average average
particle Carbon partial ESCA thickness thickness diameter number
structure dSi of surface of 2.5 of toner Kind of of represented by
value layer mm or less particles D4 organosilicon R.sup.0 formula
(1) (atomic Dav. (number Toner particles (.mu.m) compound (atoms)
(%) %) (nm) %) Toner particles 1 6.1 Methyltriethoxysilane 1 69.9
22.3 25.1 0 Toner particles 2 6.2 Ethyltriethoxysilane 2 65.2 21.6
24.3 0 Toner particles 3 6.0 Butyltriethoxysilane 4 51.6 20.3 24.9
0 Toner particles 4 6.4 Hexyltriethoxysilane 6 39.8 18.7 23.9 0
Toner particles 5 6.1 Phenyltriethoxysilane 6 28.5 18.6 25.0 0
Toner particles 6 6.2 Ethyltriethoxysilane 2 6.2 4.6 19.8 0 Toner
particles 7 6.3 Ethyltriethoxysilane 2 12.3 9.5 20.2 0 Toner
particles 8 6.1 Ethyltriethoxysilane 2 30.2 11.3 23.1 0 Toner
particles 9 6.2 Ethyltriethoxysilane 2 41.0 14.7 24.5 0 Toner
particles 10 6.2 Ethyltriethoxysilane 2 64.8 20.5 25.0 0 Toner
particles 11 6.1 Methyltriethoxysilane 1 70.0 26.0 20.3 0 Toner
particles 12 6.2 Methyltriethoxysilane 1 71.0 24.6 22.4 0 Toner
particles 13 6.1 Methyltriethoxysilane 1 70.5 23.1 25.3 0 Toner
particles 14 6.0 Methyltriethoxysilane 1 71.1 17.4 35.3 0 Toner
particles 15 6.1 Methyltriethoxysilane 1 70.7 4.2 51.6 0 Toner
particles 16 6.1 Methyltriethoxysilane 1 70.8 1.8 53.4 0 Toner
particles 17 6.2 Methyltriethoxysilane 1 69.9 22.6 25.3 0 Toner
particles 18 6.1 Methyltriethoxysilane 1 70.1 21.3 24.7 0 Toner
particles 19 6.2 Methyltriethoxysilane 1 70.2 21.6 24.2 0 Toner
particles 20 6.1 Methyltriethoxysilane 1 70.0 21.3 24.2 0 Toner
particles 21 6.0 Methyltriethoxysilane 1 70.6 22.5 25.1 0 Toner
particles 22 6.1 Methyltriethoxysilane 1 70.3 21.0 25.3 0 Toner
particles 23 6.3 Methyltriethoxysilane 1 69.8 25.8 26.1 0 Toner
particles 24 6.2 Methyltriethoxysilane 1 69.9 24.6 21.2 0 Toner
particles 25 6.1 Methyltriethoxysilane 1 70.4 26.1 20.5 0 Toner
particles 26 6.1 Methyltriethoxysilane 1 70.2 24.8 30.2 0 Toner
particles 27 6.2 Methyltriethoxysilane 1 70.3 23.1 84.3 0 Toner
particles 28 6.1 Methyltriethoxysilane 1 70.4 22.3 50.1 0 Toner
particles 29 6.2 Methyltriethoxysilane 1 70.3 6.2 5.4 18.8 Toner
particles 30 6.2 Methyltriethoxysilane 1 70.0 5.8 4.7 37.5 Toner
particles 31 6.2 Methyltriethoxysilane 1 70.1 25.1 26.1 0 Toner
particles 32 6.1 Methyltriethoxysilane 1 70.1 21.3 24.1 0 Toner
particles 33 6.1 Methyltriethoxysilane 1 70.2 17.2 86.5 0 Toner
particles 34 6.3 Methyltriethoxysilane 1 70.0 0.0 58.2 0 Toner
particles 35 6.5 Hexyltriethoxysilane 6 4.5 2.0 4.3 40.6 Toner
particles 36 6.4 Hexyltriethoxysilane 6 4.1 4.2 5.6 14.5 Toner
particles 37 6.1 Methyltriethoxysilane 1 70.2 21.3 25.3 0 Toner
particles 38 6.5 -- -- 0.0 0.0 0.0 0
TABLE-US-00009 TABLE 5 Charge Transfer latitude Image quantity
(.mu.A) density (mC/kg) After Initial/after Initial/after Example
Toner Initial endurance endurance endurance Example 1 Toner 1 2 to
20 4 to 20 1.50/1.50 -65.1/-62.3 Example 2 Toner 2 2 to 20 4 to 20
1.45/1.42 -63.6/-62.1 Example 3 Toner 3 2 to 20 6 to 18 1.45/1.42
-64.6/-55.6 Example 4 Toner 4 2 to 20 8 to 16 1.45/1.39 -60.3/-52.3
Example 5 Toner 5 2 to 20 8 to 16 1.46/1.39 -59.6/-50.3 Example 6
Toner 6 8 to 18 10 to 14 1.30/1.25 -46.5/-33.8 Example 7 Toner 7 8
to 18 8 to 14 1.35/1.26 -47.5/-40.7 Example 8 Toner 8 2 to 20 8 to
16 1.40/1.32 -55.6/-50.2 Example 9 Toner 9 2 to 20 4 to 20
1.43/1.40 -63.4/-61.5 Example 10 Toner 10 2 to 20 4 to 20 1.45/1.43
-64.2/-63.2 Example 11 Toner 11 2 to 18 4 to 16 1.29/1.25
-40.6/-31.3 Example 12 Toner 12 4 to 20 6 to 18 1.35/1.31
-60.3/-56.3 Example 13 Toner 13 2 to 20 4 to 20 1.48/1.46
-63.9/-60.8 Example 14 Toner 14 2 to 20 4 to 20 1.50/1.50
-64.1/-60.6 Example 15 Toner 15 4 to 20 4 to 20 1.50/1.50
-63.7/-62.0 Example 16 Toner 16 4 to 20 8 to 18 1.50/1.35
-64.2/-60.5 Example 17 Toner 17 4 to 14 6 to 12 1.40/1.35
-60.5/-51.2 Example 18 Toner 18 2 to 20 4 to 20 1.45/1.43
-63.5/-60.1 Example 19 Toner 19 4 to 20 4 to 20 1.50/1.48
-63.8/-60.8 Example 20 Toner 20 2 to 20 4 to 20 1.50/1.47
-65.3/-63.2 Example 21 Toner 21 2 to 20 4 to 20 1.50/1.49
-64.2/-61.3 Example 22 Toner 22 4 to 20 4 to 20 1.48/1.48
-63.5/-61.6 Example 23 Toner 23 4 to 20 4 to 20 1.42/1.38
-65.7/-63.6 Example 24 Toner 24 4 to 14 6 to 12 1.38/1.31
-54.3/-50.2 Example 25 Toner 25 6 to 14 8 to 12 1.29/1.21
-46.3/-42.6 Example 26 Toner 26 8 to 16 10 to 14 1.28/1.20
-36.8/-32.1 Example 27 Toner 27 2 to 20 4 to 20 1.45/1.45
-65.9/-64.2 Example 28 Toner 28 2 to 20 4 to 20 1.50/1.50
-64.2/-63.1 Example 29 Toner 29 6 to 18 8 to 16 1.45/1.29
-63.8/-50.6 Example 30 Toner 30 8 to 16 10 to 14 1.43/1.25
-56.3/-48.9 Example 31 Toner 31 8 to 18 10 to 14 1.35/1.28
-51.6/-46.2 Example 32 Toner 32 2 to 20 4 to 20 1.50/1.49
-63.2/-61.0 Example 33 Toner 33 2 to 20 4 to 20 1.50/1.50
-64.5/-62.7 Example 34 Toner 34 8 to 18 10 to 14 1.40/1.28
-65.8/-48.7 Comparative Toner 35 8 to 12 10 to 12 1.29/1.19
-60.3/-38.4 Example 1 Comparative Toner 36 10 to 18 10 to 12
1.35/1.28 -41.3/-32.1 Example 2 Comparative Toner 37 10 to 12 None
1.19/1.11 -33.2/-28.5 Example 3 Comparative Toner 38 4 to 20 None
1.45/1.19 -68.4/-42.1 Example 4
While the present invention has been described with reference to
exemplary embodiments, it is to be understood that the invention is
not limited to the disclosed exemplary embodiments. The scope of
the following claims is to be accorded the broadest interpretation
so as to encompass all such modifications and equivalent structures
and functions.
This application claims the benefit of Japanese Patent Application
No. 2015-079249, filed Apr. 8, 2015, which is hereby incorporated
by reference herein in its entirety.
* * * * *